Gallium-aluminum-phosphorus-oxide molecular sieve compositions

ABSTRACT

Molecular sieve compositions having three-dimensional microporous framework structures of GaO2, AlO2 and PO2 tetrahedral oxide units are disclosed. These molecular sieves have an empirical chemical composition on an anhydrous basis expressed by the formula: mR:(GaxAlyPz)O2 wherein &#34;R&#34; represents at least one organic templating agent present in the intracrystalline pore system; &#34;m&#34; represents the molar amount of &#34;R&#34; present per mole of (GaxAlyPz)O2; and &#34;x&#34;, &#34;y&#34; and &#34;z&#34; represent the mole fractions of gallium, aluminum and phosphorus, respectively, present as tetrahedral oxides. Their use as adsorbents, catalysts, etc. is also disclosed.

This application is a continuation-in-part of our copending application Ser. No. 599,771 filed Apr. 13, 1984, now abandoned.

FIELD OF THE INVENTION

The instant invention relates to a novel class of crystalline microporous molecular sieves, to the method of their preparation and to their use as adsorbents and catalysts. The invention relates to novel gallium-aluminum-phosphorus-oxide molecular sieves containing framework tetrahedral oxide units of gallium, aluminum and phosphorus. These compositions may be prepared hydrothermally from gels containing reactive compounds of gallium, aluminum and phosphorus capable of forming framework tetrahedral oxides, and preferably at least one organic templating agent which functions in part to determine the course of the crystallization mechanism and the structure of the crystalline product.

BACKGROUND OF THE INVENTION

Molecular sieves of the crystalline aluminosilicate zeolite type are well known in the art and now comprise over 150 species of both naturally occurring and synthetic compositions. In general the crystalline zeolites are formed from corner-sharing AlO₂ and SiO₂ tetrahedra and are characterized by having pore openings of uniform dimensions, having a significant ion-exchange capacity and being capable of reversibly desorbing an adsorbed phase which is dispersed throughout the internal voids of the crystal without displacing any atoms which make up the permanent crystal structure.

Other crystalline microporous compositions which are not zeolitic, i.e. do not contain AlO₂ tetrahedra as essential framework constituents, but which exhibit the ion-exchange and/or adsorption characteristics of the zeolites are also known. Metal organosilicates which are said to possess ion-exchange properties, have uniform pores and are capable of reversibly adsorbing molecules having molecular diameters of about 6 Å or less, are reported in U.S. Pat. No. 3,941,871 issued Mar. 2, 1976 to Dwyer et al. A pure silica polymorph, silicalite, having molecular sieving properties and a neutral framework containing neither cations nor cation sites is disclosed in U.S. Pat. No. 4,061,724 issued Dec. 6, 1977 to R. W. Grose et al.

A recently reported class of microporous compositions and the first framework oxide molecular sieves synthesized without silica, are the crystalline aluminophosphate compositions disclosed in U.S. Pat. No. 4,310,440 issued Jan. 12, 1982 to Wilson et al. These materials are formed from AlO₂ and PO₂ tetrahedra and have electrovalently neutral frameworks as in the case of silica polymorphs. Unlike the silica molecular sieve, silicalite, which is hydrophobic due to the absence of extra-structural cations, the aluminophosphate molecular sieves are moderately hydrophilic, apparently due to the difference in electronegativity between aluminum and phosphorus. Their intracrystalline pore volumes and pore diameters are comparable to those known for zeolites and silica molecular sieves.

In U.S. Pat. No. 4,440,871 there is described a novel class of silicon-substituted aluminophosphates which are both microporous and crystalline. The materials have a three dimensional crystal framework of PO₂ ⁺, AlO₂ ⁻ and SiO₂ tetrahedral units and, exclusive of any alkali metal or calcium which may optionally be present, an as-synthesized empirical chemical composition on an anhydrous basis of:

    mR:(Si.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Si_(x) Al_(y) P_(z))O₂ and has a value of from zero to 0.3, the maximum value in each case depending upon the molecular dimensions of the templating agent and the available void volume of the pore system of the particular silicoaluminophosphate species involved; and "x", "y", and "z" represent the mole fractions of silicon, aluminum and phosphorus, respectively, present as tetrahedral oxides. The minimum value for each of "x", "y", and "z" is 0.01 and preferably 0.02. The maximum value for "x" is 0.98; for "y" is 0.60; and for "z" is 0.52. These silicoaluminophosphates exhibit several physical and chemical properties which are characteristic of aluminosilicate zeolites and aluminophosphates.

In U.S. Pat. No. 4,500,651, there is described a novel class of titanium-containing molecular sieves whose chemical composition in the as-synthesized and anhydrous form is represented by the unit empirical formula:

    mR:(Ti.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "M" represents the moles of "R" present per mole of (Ti_(x) Al_(y) P_(z))O₂ and has a value of between zero and about 5.0; and "x", "y" and "z" represent the mole fractions of titanium, aluminum and phosphorus, respectively, present as tetrahedral oxides.

In U.S. Pat. No. 4,567,029, there is described a novel class of crystalline metal aluminophosphates having three-dimensional microporous framework structures of MO₂, AlO₂ and PO₂ tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (M_(x) Al_(y) P_(z))O₂ and has a value of from zero to 0.3; "M" represents at least one metal of the group magnesium, manganese, zinc and cobalt; "x", "y", and "z" represent the mole fractions of the metal "M", aluminum and phosphorus, respectively, present as tetrahedral oxides.

In U.S. Pat. No. 4,544,143, there is described a novel class of crystalline ferroaluminophosphates having a three-dimensional microporous framework structure of FeO₂, AlO₂ and PO₂ tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Fe.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Fe_(x) Al_(y) P_(z))O₂ and has a value of from zero to 0.3; and "x", "y" and "z" represent the mole fractions of the iron, aluminum and phosphorus, respectively, present as tetrahedral oxides.

The instant invention relates to new molecular sieve compositions having framework tetrahedral units of GaO₂ ⁻, AlO₂ ⁻ and PO₂ ⁺.

DESCRIPTION OF THE FIGURES

FIG. 1 is a ternary diagram wherein parameters relating to the instant compositions are set forth as mole fractions.

FIG. 2 is a ternary diagram wherein parameters relating to preferred compositions are set forth as mole fractions.

FIG. 3 is a ternary diagram wherein parameters relating to the reaction mixtures employed in the preparation of the compositions of this invention are set forth as mole fractions.

SUMMARY OF THE INVENTION

The instant invention relates to a new class of gallium-aluminum-phosphorus-oxide molecular sieves having a crystal framework structure of GaO₂ ⁻, AlO₂ ⁻ and PO₂ ⁺ tetrahedral oxide units. These new molecular sieves exhibit ion-exchange, adsorption and catalytic properties and, accordingly, find wide use as adsorbents and catalysts. The members of this novel class of compositions have crystal framework structures of GaO₂ ⁻, AlO₂ ⁻ and PO₂ ⁺ tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Ga.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Ga_(x) Al_(y) P_(z))O₂ and has a value of zero to about 0.3; and "x", "y" and "z" represent the mole fractions of gallium, aluminum and phosphorus, respectively, present as tetrahedral oxides. These molecular sieve compositions comprise crystalline molecular sieves having a three-dimensional microporous framework structure of GaO₂ ⁻, AlO₂ ⁻ and PO₂ ⁺ tetrahedral units.

The molecular sieves of the instant invention will be generally referred to by the acronym "GaAPO" to designate the framework of GaO₂ ⁻, AlO₂ ⁻ and PO₂ ⁺ tetrahedral units. Actual class members will be identified by denominating the various structural species which make up the GaAPO class by assigning a number and, accordingly, are identified as "GaAPO-i" wherein "i" is an integer. The given species designation is not intended to denote a similarity in structure to any other species denominated by a numbering system.

DETAILED DESCRIPTION OF THE INVENTION

The instant invention relates to a new class of gallium-aluminum-phosphorus-oxide molecular sieves comprising a crystal framework structure of GaO₂ ⁻, AlO₂ ⁻ and PO₂ ⁺ tetrahedral oxide units. These new molecular sieves exhibit ion-exchange, adsorption and catalytic properties and, accordingly, find wide use as adsorbents and catalysts.

The GaAPO molecular sieves have three-dimensional microporous framework structures of GaO₂ ⁻, AlO₂ ⁻, and PO₂ ⁺ tetrahedral oxide units having an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Ga.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Ga_(x) Al_(y) P_(z))O₂ and has a value of zero to about 0.3 but is preferably not greater than about 0.15; and "x", "y" and "z" represent the mole fractions of gallium, aluminum and phosphorus, respectively, present as tetrahedral oxides. The mole fractions "x", "y", and "z" are generally defined as being within the hexagonal compositional area defined by points A, B, C, D, E and F of the ternary diagram of FIG. 1. Points A, B, C, D, E and F of FIG. 1 have the following values for "x", "y", and "z":

    ______________________________________                                                Mole Fraction                                                           Point    x             y      z                                                ______________________________________                                         A        0.01          0.60   0.39                                             B        0.01          0.34   0.65                                             C        0.34          0.01   0.65                                             D        0.60          0.01   0.39                                             E        0.60          0.39   0.01                                             F        0.39          0.60   0.01                                             ______________________________________                                    

In general, the value of "z" in the GaAPO molecular sieves will be not greater than 0.60, so that the compositions will lie within the hexagonal compositional area defined by points A, M, N, D, E and F of the ternary diagram of FIG. 1, where points M and N have the following values for "z", "y", and "z":

    ______________________________________                                                Mole Fraction                                                           Point    x             y      z                                                ______________________________________                                         M        0.01          0.39   0.60                                             N        0.39          0.01   0.60                                             ______________________________________                                    

In a preferred subclass of the GaAPO molecular sieves the values of "x", "y" and "z" in the above formula are within the tetragonal compositional area defined by the points a, b, c and d of the ternary diagram which is FIG. 2 of the drawings, said points a, b, c and d representing the following values for "x", "y" and "z":

    ______________________________________                                                Mole Fraction                                                           Point    x             y      z                                                ______________________________________                                         a        0.01          0.59   0.40                                             b        0.01          0.34   0.65                                             c        0.34          0.01   0.65                                             d        0.59          0.01   0.40                                             ______________________________________                                    

In an especially preferred subclass of the GaAPO molecular sieves the values "x", "y" and "z" in the formula are within the hexagonal compositional area defined by the points, e, f, g, h, i and j of the ternary diagram which is FIG. 2 of the drawings, said points e, f, g, h, i and j representing the following values for "x", "y" and "z":

    ______________________________________                                                Mole Fraction                                                           Point    x             y      z                                                ______________________________________                                         e        0.03          0.52   0.45                                             f        0.03          0.33   0.64                                             g        0.16          0.20   0.64                                             h        0.25          0.20   0.55                                             i        0.25          0.33   0.42                                             j        0.06          0.52   0.42                                             ______________________________________                                    

In GaAPOs of this invention are useful as adsorbents, catalysts, ion-exchangers, and the like in much the same fashion as aluminosilicates have been employed heretofore, although their chemical and physical properties are not necessarily similar to those observed for aluminosilicates.

GaAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of gallium, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure, at a temperature between 50° and 250° C., and preferably between 100° C. and 200° C. until crystals of the GaAPO product are obtained, usually a period of from several hours to several weeks. Typical crystallization times are from about 2 hours to about 30 days, with from about 4 hours to about 20 days, and preferably about 1 to about 7 days, being generally employed to obtain crystals of the GaAPO products. The product is recovered by any convenient method such as centrifugation or filtration.

In synthesizing the GaAPO compositions of the instant invention, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:

    aR:(Ga.sub.u Al.sub.v P.sub.w)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6 and most preferably not more than about 1.0; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably between about 2 and about 20; and --u--, --v-- and --w-- represent the mole fractions of gallium, aluminum and phosphorus, respectively, and each has a value of at least 0.01. The mole fractions --u--, --v-- and --w-- in the reaction mixture are preferably within the pentagonal compositional area defined by points G, H, I, J and K which is shown in FIG. 3 of the drawings, where points G, H, I, J and K have the following values for --u--, --v-- and --w--:

    ______________________________________                                                Mole Fraction                                                           Point    u             v      w                                                ______________________________________                                         G        0.01          0.60   0.39                                             H        0.01          0.39   0.60                                             I        0.39          0.01   0.60                                             J        0.98          0.01   0.01                                             K        0.39          0.60   0.01                                             ______________________________________                                    

In especially preferred reaction mixtures, from 0.2 to 0.5 mole of Ga₂ O₃ and from 0.3 to 1 mole of Al₂ O₃ are present for each mole of P₂ O₅.

In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of u+v+w=1.00 mole, whereas in the examples the reaction mixtures are expressed in terms of the molar oxide ratios and may be normalized to 1.00 mole of P₂ O₅ or Al₂ O₃ This latter form is readily converted to the former form by routine calculation by dividing the total number of moles of gallium, aluminum and phosphorus into the moles of each of gallium, aluminum and phosphorus. The moles of template and water are similarly normalized by dividing by the total moles of gallium, aluminum and phosphorus.

In forming the reaction mixture from which the instant molecular sieves are formed the organic templating agent can be any of those heretofore proposed for use in the synthesis of conventional zeolite aluminosilicates. In general these compounds contain elements of Group VA of the Periodic Table of Elements, particularly nitrogen, phosphorus, arsenic and antimony, preferably nitrogen or phosphorus and most preferably nitrogen, which compounds also contain at least one alkyl or aryl group having from 1 to 8 carbon atoms. Particularly preferred compounds for use as templating agents are the amines, quaternary phosphonium and quaternary ammonium compounds, the latter being represented generally by the formula R₄ X⁺ wherein "X" is nitrogen or phosphorus and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms. Polymeric quaternary ammonium salts such as [(C₁₄ H₃₂ N₂)(OH)₂ ]_(x) wherein "x" has a value of at least 2 are also suitably employed. The mono-, di- and tri-amines are advantageously utilized, either alone or in combination with a quaternary ammonium compound or other templating compound. Mixtures of two or more templating agents can either produce mixtures of the desired GaAPOs or the more strongly directing templating species may control the course of the reaction with the other templating species serving primarily to establish the pH conditions of the reaction gel. Representative templating agents include tetramethylammonium, tetraethylammonium, tetrapropylammonium or tetrabutylammonium ions; tetrapentylammonium ion; di-n-propylamine; tripropylamine; triethylamine; triethanolamine; piperidine; cyclohexylamine; 2-methylpyridine; N,N-dimethylbenzylamine; N,N-dimethylethanolamine; choline; N,N'-dimethylpiperazine; 1,4-diazabicyclo (2,2,2,) octane; N-methyldiethanolamine, N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine; N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine; quinuclidine; N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion; di-n-butylamine, neopentylamine; di-n-pentylamine; isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; and 2-imidazolidone. Not every templating agent will direct the formation of every species of GaAPO, i.e., a single templating agent can, with proper manipulation of the reaction condition, direct the formation of several GaAPO compositions, and a given GaAPO composition can be produced using several different templating agents.

The reactive phosphorus source is preferably phosphoric acid, but organic phosphates such as triethyl phosphate may be satisfactory, and so also may crystalline or amorphous aluminophosphates such as the AlPO₄ composition of U.S. Pat. No. 4,310,440. Organo-phosphorus compounds, such as tetrabutylphosphonium bromide, do not apparently serve as reactive sources of phosphorus, but these compounds may function as templating agents. Conventional phosphorus salts such as sodium metaphosphate, may be used, at least in part, as the phosphorus source, but are not preferred.

The preferred aluminum source is either an aluminum alkoxide, such as aluminum isoproproxide, or pseudoboehmite. The crystalline or amorphous aluminophosphates which are a suitable source of phosphorus are, of course, also suitable sources of aluminum. Other sources of aluminum used in zeolite synthesis, such as gibbsite, sodium aluminate and aluminum trichloride, can be employed but are not preferred.

The reactive source of gallium can be introduced into the reaction system in any form which permits the formation in situ of a reactive form of gallium, i.e., reactive to form the framework tetrahedral oxide unit of gallium. Compounds of gallium which may be employed include oxides, alkoxides, hydroxides, chlorides, bromides, iodides, nitrates, sulfates, carboxylates (e.g., acetates) and the like.

While not essential to the synthesis of GaAPO compositions, stirring or other moderate agitation of the reaction mixture and/or seeding the reaction mixture with seed crystals of either the GaAPO species to be produced or a topologically similar aluminophosphate, aluminosilicate or molecular sieve composition, facilitates the crystallization procedure.

After crystallization the GaAPO product may be isolated and advantageously washed with water and dried in air. The as-synthesized GaAPO generally contains within its internal pore system at least one form of the templating agent employed in its formation. Most commonly the organic moiety is present, at least in part, as a charge-balancing cation as is generally the case with as-synthesized aluminosilicate zeolites prepared from organic-containing reaction systems. It is possible, however, that some or all of the organic moiety is an occluded molecular species in a particular GaAPO species. As a general rule the templating agent, and hence the occluded organic species, is too large to move freely through the pore system of the GaAPO product and must be removed by calcining the GaAPO at temperatures of 200° C. to 700° C., preferably about 350° C. to about 600° C., to thermally degrade the organic species. In a few instances the pores of the GaAPO product are sufficiently large to permit transport of the templating agent, particularly if the latter is a small molecule, and accordingly complete or partial removal thereof can be accomplished by conventional desorption procedures such as carried out in the case of zeolites. It will be understood that the term "as synthesized" as used herein does not include the condition of the GaAPO phase wherein the organic moiety occupying the intracrystalline pore system as a result of the hydrothermal crystalline process has been reduced by post-synthesis treatment such that the value of "m" in the composition formula

    mR:(Ga.sub.x Al.sub.y P.sub.z)O.sub.2

has a value of less than 0.02. The other symbols of the formula are as defined hereinabove. In those preparations in which an alkoxide is employed as the source of gallium, aluminum or phosphorus, the corresponding alcohol is necessarily present in the reaction mixture since it is a hydrolysis product of the alkoxide. It has not been determined whether this alcohol participates in the synthesis process as a templating agent. For the purposes of this application, however, this alcohol is arbitrarily omitted from the class of templating agents, even if it is present in the as-synthesized GaAPO material.

Since the present GaAPO compositions are formed from GaO₂ AlO₂, PO₂, tetrahedral units which, respectively, have a net charge of -1, -1 and +1, the matter of cation exchangeability is considerably more complicated than in the case of zeolitic molecular sieves in which, ideally, there is a stoichiometric relationship between AlO₂ ⁻ tetrahedra and charge-balancing cations. In the instant compositions, an AlO₂ ⁻ tetrahedron can be balanced electrically either by association with a PO₂ ⁺ tetrahedron or a simple cation such as an alkali metal cation, a proton (H⁺), a cation of gallium present in the reaction mixture, or an organic cation derived from the templating agent. Similarly, a GaO₂ ⁻ tetrahedron can be balanced electrically by association with PO₂ ⁺ tetrahedra, a cation of gallium present in the reaction mixture, a simple cation such as an alkali metal cation, a proton (H⁺), organic cations derived from the templating agent, or other divalent or polyvalent metal cations introduced from an extraneous source. It has also been postulated that non-adjacent AlO₂ ⁻ and PO₂ ⁺ tetrahedral pairs can be balanced by Na⁺ and OH⁻ respectively [Flanigen and Grose, Molecular Sieve Zeolites-I, ACS, Washington, D.C. (1971)].

The GaAPO compositions of the present invention may exhibit cation-exchange capacity when analyzed using ion-exchange techniques heretofore employed with zeolitic aluminosilicates and have pore diameters which are inherent in the lattice structure of each species and which are at least about 3 Å in diameter. Ion exchange of GaAPO compositions would ordinarily be possible only after any organic moiety derived from the template, present as a result of synthesis, has been removed from the pore system. Dehydration to remove water present in the as-synthesized GaAPO compositions can usually be accomplished, to some degree at least, in the usual manner without removal of the organic moiety, but the absence of the organic species greatly facilitates adsorption and desorption procedures. The GaAPO materials have various degrees of hydrothermal and thermal stability, some being quite remarkable in this regard, and function well as molecular sieve adsorbents and hydrocarbon conversion catalysts or catalyst bases.

In preparing the GaAPO composition it is preferred to use a stainless steel reaction vessel lined with an inert plastic material, e.g., polytetrafluoroethylene, to avoid contamination of the reaction mixture. In general, the final reaction mixture from which each GaAPO composition is crystallized is prepared by forming mixtures of less than all of the reagents and thereafter incorporating into these mixtures additional reagents either singly or in the form of other intermediate mixtures of two or more reagents. In some instances the reagents admixed retain their identity in the intermediate mixture and in other cases some or all of the reagents are involved in chemical reactions to produce new reagents. The term "mixture" is applied in both cases. Further, it is preferred that the intermediate mixtures as well as the final reaction mixtures be stirred until substantially homogeneous.

X-ray patterns of reaction products are obtained by X-ray analysis using standard X-ray powder diffraction techniques. The radiation source is a high-intensity, copper target, X-ray tube operated at 50 Kv and 40 ma. The diffraction pattern from the copper K-alpha radiation and graphite monochromator is suitably recorded by an X-ray spectrometer scintillation counter, pulse height analyzer and strip chart recorder. X-ray patterns are obtained using flat compressed powder samples which are scanned at 2° (2 theta) per minute, using a two second time constant. Interplanar spacings (d) in Angstrom units are obtained from the position of the diffraction peaks expressed as 2θ where θ is the Bragg angle as observed on the strip chart. Intensities are determined from the heights of diffraction peaks after subtracting background, "I_(o) "being the intensity of the strongest line or peak, and "I" being the intensity of each of the other peaks. Alternatively, the X-ray patterns may be obtained by use of computer based techniques using copper K alpha radiation, Siemens type K-805 X-ray sources and Siemens D-500 X-ray powder diffractometers, available from Siemens Corporation, Cherry Hill, N.J.

As will be understood by those skilled in the art the determination of the parameter 2 theta is subject to both human and mechanical error, which in combination, can impose an uncertainty of about ±0.4° on each reported value of 2 theta. This uncertainty is, of course, also manifested in the reported values of the d-spacings, which are calculated from the 2 theta values. This imprecision is general throughout the art and is not sufficient to preclude the differentiation of the present crystalline materials from each other and from the compositions of the prior art. In some of the X-ray patterns reported, the relative intensities of the d-spacings are indicated by the notations vs, s, m, w and vw which represent very strong, strong, medium, weak and very weak, respectively.

In certain instances the purity of a synthesized product may be assessed with reference to its X-ray powder diffraction pattern. Thus, for example, if a sample is stated to be pure, it is intended only that the X-ray pattern of the sample is free of lines attributable to crystalline impurities, not that there are no amorphous materials present.

The molecular sieves of the instant invention may be characterized by their X-ray powder diffraction patterns and as such may have one of the X-ray patterns set forth in the following Tables A through V, wherein said X-ray patterns are for the as-synthesized form unless otherwise noted. In most cases, the pattern of the corresponding calcined form will also fall within the relevant Table. However, in some cases the removal of the occluded templating agent which occurs during calcination will be accompanied by sufficient relaxation of the lattice to shift some of the lines slightly outside the ranges specified in the relevant Table. In a small number of cases (e.g. GaAPO-33), calcination appears likely to cause more substantial distortions in the crystal lattice, and hence more significant changes in the X-ray power diffraction pattern.

                  TABLE A                                                          ______________________________________                                         (GaAPO-5)                                                                      2θ     d(Å)  Relative Intensity                                      ______________________________________                                          7.3-7.65     12.1-11.56                                                                              m-vs                                                    19.5-20.0    4.55-4.44 m-s                                                     20.9-21.3    4.25-4.17 m-vs                                                    22.2-22.7    4.00-3.92 w-vs                                                    25.7-26.2    3.47-3.40 w-m                                                     ______________________________________                                    

                  TABLE B                                                          ______________________________________                                         (GaAPO-11)                                                                     2θ     d(Å) Relative Intensity                                       ______________________________________                                          9.3-9.65    9.51-9.17                                                                               m-s                                                      20.2-20.6    4.40-4.31                                                                               m-s                                                      20.9-21.3    4.25-4.17                                                                                s-vs                                                    22.0-22.5    4.04-3.95                                                                               m-s                                                      22.5-22.9    3.95-3.92                                                                               m-s                                                      23.0-23.4    3.85-3.80                                                                                m-vs                                                    ______________________________________                                    

                  TABLE C                                                          ______________________________________                                         (GaAPO-14)                                                                     2θ     d(Å) Relative Intensity                                       ______________________________________                                         8.9-9.1      9.89-9.77                                                                               vs                                                       12.9-13.3    6.86-6.67                                                                               w-m                                                      15.7-15.8    5.66-5.61                                                                               w-m                                                      17.7-18.1    5.02-4.91                                                                               w-m                                                      22.2-22.8    4.00-3.89                                                                               w                                                        27.1-27.2    3.30-3.28                                                                               w                                                        ______________________________________                                    

                  TABLE D                                                          ______________________________________                                         (GaAPO-16)                                                                     2θ     d(Å)  Relative Intensity                                      ______________________________________                                         11.3-11.6    7.83-7.63  m-vs                                                   18.7-18.9    4.75-4.70 w-s                                                     21.9-22.3    4.06-3.99  m-vs                                                   26.5-27.0    3.363-3.302                                                                              w-m                                                      29.7-30.05  3.008-2.974                                                                              w-m                                                     ______________________________________                                    

                  TABLE E                                                          ______________________________________                                         (GaAPO-17)                                                                     2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.7-7.8      11.5-11.3 vs                                                      13.3-13.5    6.65-6.57  s-vs                                                   15.4-15.6    5.75-5.69 m-vs                                                    19.5-19.7    4.55-4.51 m-vs                                                    20.5-20.6    4.33-4.31 vs                                                       31.7-32.00  2.819-2.797                                                                              w-s                                                     ______________________________________                                    

                  TABLE F                                                          ______________________________________                                         (GaAPO-18)                                                                     2θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.5-9.7      9.27-9.14 vs                                                      15.5-15.7    5.73-5.64 w-m                                                     16.9-17.1    5.25-5.19 m                                                       20.15-20.25  4.41-4.39 m                                                       20.95-21.1   4.24-4.22 w-m                                                     31.8-32.5    2.814-2.755                                                                              m                                                       ______________________________________                                    

                  TABLE G                                                          ______________________________________                                         (GaAPO-20)                                                                     2θ      d(Å) Relative Intensity                                      ______________________________________                                          13.7-14.25   6.46-6.22                                                                               m-vs                                                    19.55-20.0    4.54-4.44                                                                               w-s                                                     24.05-24.6    3.70-3.63                                                                               m-vs                                                    28.3-28.5     3.16-3.13                                                                               w-m                                                     34.8-35.2     2.58-2.55                                                                               w                                                       ______________________________________                                    

                  TABLE H                                                          ______________________________________                                         (GaAPO-26)                                                                     2θ     d(Å) Relative Intensity                                       ______________________________________                                         8.2-8.3      10.8-10.7                                                                               w-vs                                                     9.6-9.9      9.2-9.0  vw-m                                                     10.5-10.6    8.45-8.35                                                                               w-vs                                                     21.8-22.1    4.07-4.01                                                                               w-vs                                                     22.5-22.7    3.95-3.92                                                                               w-s                                                      28.6-28.9    3.12-3.09                                                                               vw-m                                                     ______________________________________                                    

                  TABLE I                                                          ______________________________________                                         (GaAPO-31)                                                                     2θ     d(Å)  Relative Intensity                                      ______________________________________                                         8.5-8.6      10.40-10.28                                                                              m-s                                                     20.2-20.3    4.40-4.37 m                                                       21.9-22.1    4.06-4.02 w-m                                                     22.6-22.7    3.93-3.92 vs                                                      31.7-31.8    2.823-2.814                                                                              w-m                                                     ______________________________________                                    

                  TABLE J*                                                         ______________________________________                                         (GaAPO-33)                                                                     2θ      d(Å) Relative Intensity                                      ______________________________________                                         9.25-9.55     9.56-9.26                                                                               w-m                                                     12.5-12.9     7.08-6.86                                                                               vs                                                      16.9-17.3     5.25-5.13                                                                               w-m                                                     20.45-20.9    4.34-4.25                                                                               w-m                                                     23.85-24.25   3.73-3.67                                                                               w-m                                                     26.05-26.35   3.42-3.38                                                                               w-m                                                     27.3-27.6     3.27-3.23                                                                               vs                                                      ______________________________________                                          *as-synthesized form                                                     

                  TABLE K*                                                         ______________________________________                                         (GaAPO-33)                                                                     2θ      d(Å) Relative Intensity                                      ______________________________________                                         13.15-13.4    6.73-6.61                                                                               vs                                                      18.05-18.35   4.91-4.83                                                                               m                                                       18.4-18.6     4.82-4.77                                                                               m                                                       26.55-26.7    3.36-3.34                                                                               m                                                       32.0-32.1     2.80-2.79                                                                               m                                                       ______________________________________                                          *calcined form                                                           

                  TABLE L                                                          ______________________________________                                         (GaAPO-34)                                                                     2θ      d(Å) Relative Intensity                                      ______________________________________                                          9.4-9.65     9.41-9.17                                                                                 s-vs                                                  15.9-16.2     5.57-5.47                                                                               vw-m                                                    17.85-18.4    4.97-4.82                                                                               w-s                                                     20.3-20.9     4.37-4.25                                                                                m-vs                                                   24.95-25.4    3.57-3.51                                                                               vw-s                                                    30.3-30.8     2.95-2.90                                                                               w-s                                                     ______________________________________                                    

                  TABLE M                                                          ______________________________________                                         (GaAPO-35)                                                                     2θ     d(Å)  Relative Intensity                                      ______________________________________                                         10.8-11.1    8.19-7.97 m                                                       17.2-17.4    5.16-5.10  s-vs                                                    21.0-21.25  4.23-4.18 m-s                                                     21.8-22.0    4.08-4.04 vs                                                      31.8-32.2    2.814-2.788                                                                              m                                                       ______________________________________                                    

                  TABLE N                                                          ______________________________________                                         (GaAPO-36)                                                                     2θ     d(Å) Relative Intensity                                       ______________________________________                                         7.7-7.9      11.5-11.2                                                                               vs                                                       16.2-16.6    5.47-5.34                                                                               w-m                                                      18.9-19.3    4.70-4.60                                                                               m-s                                                      27.4-27.7    3.26-3.22                                                                               w-m                                                      27.7-28.0    3.22-3.19                                                                               w-m                                                      ______________________________________                                    

                  TABLE O                                                          ______________________________________                                         (GaAPO-37)                                                                     2θ     d(Å)  Relative Intensity                                      ______________________________________                                         6.1-6.3      14.49-14.03                                                                              vs                                                      15.5-15.7    5.72-5.64 w-m                                                     18.5-18.8    4.80-4.72 w-m                                                     23.5-23.7    3.79-3.75 w-m                                                     26.9-27.1    3.31-3.29 w-m                                                     ______________________________________                                    

                  TABLE P                                                          ______________________________________                                         (GaAPO-39)                                                                     2θ     d(Å) Relative Intensity                                       ______________________________________                                         9.4-9.6      9.41-9.21                                                                               w-m                                                      13.3-13.6    6.66-6.51                                                                                m-vs                                                    18.0-18.4    4.93-4.82                                                                               m                                                        21.2-21.5    4.19-4.13                                                                               m-s                                                      22.5-23.0    3.95-3.87                                                                                s-vs                                                    30.2-30.5    2.96-2.93                                                                               w-m                                                      ______________________________________                                    

                  TABLE Q                                                          ______________________________________                                         (GaAPO-40)                                                                     2θ    d(Å)  Relative Intensity                                       ______________________________________                                         7.5-7.7     11.79-11.48                                                                              vw-m                                                     8.0-8.1     11.05-10.94                                                                              s-vs                                                     12.4-12.5   7.14-7.08 w-vs                                                     13.6-13.8   6.51-6.42 m-s                                                      14.0-14.1   6.33-6.28 w-m                                                      27.8-28.0   3.209-3.187                                                                              w-m                                                      ______________________________________                                    

                  TABLE R                                                          ______________________________________                                         (GaAPO-41)                                                                     2θ    d(Å)  Relative Intensity                                       ______________________________________                                         13.6-13.8   6.51-6.42 w-m                                                      20.5-20.6   4.33-4.31 w-m                                                      21.1-21.3   4.21-4.17 vs                                                       22.1-22.3   4.02-3.99 m-s                                                      22.8-23.0   3.90-3.86 m                                                        23.1-23.4   3.82-3.80 w-m                                                      25.5-25.9   3.493-3.440                                                                              w-m                                                      ______________________________________                                    

                  TABLE S                                                          ______________________________________                                         (GaAPO-42)                                                                     2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.15-7.4     12.36-11.95                                                                              m-vs                                                    12.5-12.7    7.08-6.97 m-s                                                     21.75-21.9   4.09-4.06 m-s                                                      24.1-24.25  3.69-3.67 vs                                                      27.25-27.4   3.273-3.255                                                                              s                                                       30.05-30.25  2.974-2.955                                                                              m-s                                                     ______________________________________                                    

                  TABLE T                                                          ______________________________________                                         (GaAPO-44)                                                                     2θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.4-9.55     9.41-9.26 vs                                                      13.0-13.1    6.81-6.76 w-m                                                     16.0-16.2    5.54-5.47 w-m                                                     20.6-20.85   4.31-4.26 s-vs                                                    24.3-24.4    3.66-3.65 w-vs                                                    30.7-30.95   2.912-2.889                                                                              w-s                                                     ______________________________________                                    

                  TABLE U                                                          ______________________________________                                         (GaAPO-46)                                                                     2θ    d(Å)  Relative Intensity                                       ______________________________________                                         7.2-8.1     12.3-10.9 vs                                                       21.2-21.8   4.19-4.08 w-m                                                      22.5-23.0   3.95-3.87 vw-m                                                     26.6-27.2   3.351-3.278                                                                              vw-w                                                     28.5-29.0   3.132-3.079                                                                              vw-w                                                     ______________________________________                                    

                  TABLE V                                                          ______________________________________                                         (GaAPO-47)                                                                     2θ    d(Å)  Relative Intensity                                       ______________________________________                                         9.4         9.41      vs                                                       15.9-16.0   5.57-5.54 w-m                                                      20.5-20.6   4.33-4.31 s                                                        24.5-24.7   3.63-3.60 w                                                        25.8-25.9   3.45-3.44 w                                                        30.4-30.5   2.940-2.931                                                                              w                                                        ______________________________________                                    

The following examples are provided to further illustrate the invention and are not intended to be limiting thereof:

EXAMPLE 1 (PREPARATION OF GAAPO-5)

a) To prepare GaAPO-5, a reaction mixture was formed by combining 6.6 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄) with 6.5 grams of water, adding to the resultant mixture 2.9 grams of hydrated aluminum oxide in the form of a pseudo-boehmite phase comprising 75.1 wt. percent of Al₂ O₃ and 24.9 wt. percent H₂ O, and stirring the resultant mixture until it was homogeneous. To this homogeneous mixture was added with stirring a solution prepared by dissolving 4.6 grams of gallium(III) sulfate hydrate (Ga₂ (SO₄)₃.12.2H₂ O) in 9.2 grams of water. Finally, there were added to the reaction mixture 12.3 grams of tri-n-propylamine (TPA), and the resultant mixture was stirred until homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

3.0 TPA:0.25 Ga₂ O₃ :0.75 Al₂ O₃ 1.0 P₂ O₅ :0.75 H₂ SO₄ :40 H₂ O.

An aliquot of this final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 150° C. under autogeneous pressure for 73 hours. The solid reaction product (which was determined by the analyses described below to be principally GaAPO-5) was recovered by centrifugation, washed with water and dried in air at ambient temperature.

The X-ray powder diffraction pattern of the major component of the product, as synthesized, was characterized by the data in the following Table AA (Hereinafter Tables designated AA, AB, etc., represent Tables containing all the peaks set forth in Table A above, and similarly for Tables CA, CB, etc.):

                  TABLE AA                                                         ______________________________________                                         (GaAPO-5)                                                                                          Relative Intensity                                         2θ    d (Å)                                                                              100 × I/I.sub.o                                      ______________________________________                                         7.4         11.9    100                                                        12.9        6.86    10                                                         14.9        5.95    20                                                         19.8        4.48    38                                                         21.0        4.23    48                                                         22.4        3.97    62                                                         24.7        3.60     3                                                         26.0        3.43    24                                                         29.0        3.08    11                                                         30.1        2.97    17                                                         33.7        2.660    3                                                         34.6        2.592   13                                                         37.0        2.430    3                                                         37.7        2.386    9                                                         41.7        2.165    2                                                         42.2        2.141    2                                                         47.8        1.903    4                                                         ______________________________________                                    

Scanning electron microscopy of the solid product showed numerous crystals approximately 20 microns in diameter with a morphology corresponding to that expected for GaAPO 5. Electron microprobe spot analysis of these crystals indicated the following approximate composition:

    Ga.sub.0.05 Al.sub.0.35 P.sub.0.60

thus indicating that the product contained gallium, aluminum and phosphorus in amounts within the hexagonal compositional area defined by points A, B, C, D, E and F of FIG. 1.

EXAMPLE 2 (PREPARATION OF GAAPO-5)

a) To prepare GaAPO-5, a reaction mixture was formed by combining 11.5 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄) with 14.8 grams of water, adding to the resultant mixture 5.1 grams of hydrated aluminum oxide in the form of a pseudo-boehmite phase comprising 75.1 wt. percent of Al₂ O₃ and 24.9 wt. percent H₂ O, and stirring the resultant mixture until it was homogeneous. To this homogeneous mixture was added with stirring a slurry of 2.7 grams of gallium(III) hydroxide (86.4 percent Ga₂ O₃, 13.5 percent H₂ O) in 25.4 grams of 40 percent aqueous tetra-n-propylammonium hydroxide (TPAOH) and the resultant mixture was stirred until homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

1.0 TPAOH:0.25 Ga₂ O₃ :0.75 Al₂ O₃ :1.0 P₂ O₅ :40 H₂ O.

An aliquot of this final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 150° C. under autogeneous pressure for 72 hours. The solid reaction product (which was determined by the analyses described below to be principally GaAPO-5) was recovered by a combination of filtration and centrifugation and dried in air at ambient temperature.

The X-ray powder diffraction pattern of the major component of the product, as synthesized, was essentially that set forth in Table AA above.

Scanning electron microscopy of the solid product showed numerous crystals with a morphology corresponding to that expected for GaAPO-5. Electron microprobe spot analysis of these crystals indicated the following approximate composition:

    Ga.sub.0.15 Al.sub.0.40 P.sub.0.45

thus indicating that the product contained gallium, aluminum and phosphorus in amounts within the hexagonal compositional area defined by points A, B, C, D, E and F of FIG. 1.

EXAMPLE 3 (PREPARATION OF GAAPO-5)

a) To prepare GaAPO-5, a reaction mixture was formed by combining 9.2 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄) with 15.1 grams of water, adding to the resultant mixture 4.1 grams of hydrated aluminum oxide in the form of a pseudo-boehmite phase comprising 75.1 wt. percent of Al₂ O₃ and 24.9 wt. percent H₂ O, and stirring the resultant mixture until it was homogeneous. To this homogeneous mixture was added with stirring 2.2 grams of gallium(III) hydroxide (86.4 percent Ga₂ O₃, 13.5 percent H₂ O) partially dissolved in 14.7 grams of 40 percent aqueous tetraethylammonium hydroxide (TEAOH) and the resultant mixture was stirred until homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

1.0 TEAOH:0.25 Ga₂ O₃ :0.75 Al₂ O₃ :1.0 P₂ O₅ :40 H₂ O.

An aliquot of this final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 150° C. under autogeneous pressure for 24 hours. The solid reaction product (which was determined by the analyses described below to be principally GaAPO-5) was recovered by filtration, washed with water and dried in air at ambient temperature.

The X-ray powder diffraction pattern of the major component of the product, as synthesized, was essentially that set forth in Table AA above.

All the GaAPO-5 compositions prepared in

Examples 1-3 had similar X-ray powder diffraction patterns. The following general Table AB summarizes the X-ray powder diffraction lines which were obtained from the various specimens of GaAPO-5; the least intense lines were not obtained from every specimen.

                  TABLE AB                                                         ______________________________________                                         (GaAPO-5)                                                                                            Relative Intensity                                       2θ    d(Å)  100 × I/I.sub.o                                    ______________________________________                                         7.4-7.6     11.9-11.7 100                                                      12.9-13.1   6.86-6.78  8-10                                                    14.9-15.1   5.95-5.86 15-26                                                    19.8-20.0   4.49-4.44 36-55                                                    21.0-21.3   4.24-4.18 31-52                                                    22.4-22.7   3.97-3.92 47-69                                                    24.5-25.0   3.64-3.56 2-3                                                      26.0-26.2   3.43-3.40 17-28                                                    29.0-29.3   3.08-3.04  8-13                                                    30.1-30.3   2.969-2.945                                                                               9-17                                                    33.7        2.662     3                                                        34.6-34.9   2.592-2.574                                                                               8-13                                                    37.0        2.428     3                                                        37.7-38.0   2.388-2.366                                                                              6-9                                                      41.7        2.165     2                                                        42.2        2.140     2                                                        47.8        1.901     4                                                        ______________________________________                                    

EXAMPLE 4 (PREPARATION OF GAAPO-11)

a) GaAPO-11 is prepared from a reaction mixture having a composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture, of:

1.0-2.0 DPA:0.05-0.2 Ga₂ O₃ :0.5-1.0 Al₂ O₃ 0.5-1.0 P₂ O₅ :40-100 H₂ O

where "DPA" denotes di-n-propylamine.

The reaction mixture is digested by placing the reaction mixture in a sealed stainless steel pressure vessel and heating it at an effective temperature and for an effective time until crystals of the GaAPO-11 product are obtained. Solids are then recovered by filtration, washed with water and dried in air at room temperature.

The GaAPO-11 product's chemical analysis shows the GaAPO-11 product contains gallium, aluminum and phosphorus in amounts within the hexagonal compositional area defined by points A, B, C, E and F of FIG. 1.

The X-ray powder diffraction pattern of a GaAPO-11 product is characterized by the following data:

    ______________________________________                                         2θ     d(Å) Relative Intensity                                       ______________________________________                                          9.3-9.65    9.51-9.17                                                                               m-s                                                      20.2-20.6    4.40-4.31                                                                               m-s                                                      20.9-21.3    4.25-4.17                                                                               s-vs                                                     22.0-22.5    4.04-3.95                                                                               m-s                                                      22.5-22.9    3.95-3.92                                                                               m-s                                                      23.0-23.4    3.85-3.80                                                                               m-vs                                                     ______________________________________                                    

b) The X-ray powder diffraction pattern for a calcined GaAPO-11 is also characterized by the X-ray pattern of part a).

c) When the calcined GaAPO-11 of part (b) is utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus the measurements are made on a sample after activation at 350° C. in vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                  Kinetic    Pressure         Wt. %                                     Adsorbate                                                                               Diameter(Å)                                                                           (Torr)   Temp, °C.                                                                       Adsorbed*                                 ______________________________________                                         O.sub.2  3.46       100      -183    5                                         O.sub.2  3.46       750      -183    6                                         Cyclohexane                                                                             6.0        90       24      4                                         H.sub.2 O                                                                               2.65       4.3      24      6                                         H.sub.2 O                                                                               2.65       20       24      8                                         ______________________________________                                          *typical amount adsorbed                                                 

The pore diameter of GaAPO-11 is about 6 Å.

EXAMPLE 5 (PREPARATION OF GAAPO-17)

a) To prepare GaAPO-17, a reaction mixture was formed by combining 4.1 grams of hydrated aluminum oxide (in the form of a pseudo-boehmite phase comprising 75.1 wt. percent of Al₂ O₃ and 24.9 wt. percent H₂ O) with a mixture of 6.5 grams of gallium(III) sulfate hydrate (Ga₂ (SO₄)₃.12.2H₂ O) in 10.5 grams of water. There was then added to the reaction mixture a solution formed by mixing 9.2 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄) with a solution of 13.3 grams of quinuclidine (QN) in 23.3 grams of water, and the resultant mixture was stirred until homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

3.0 QN:0.25 Ga₂ O₃ :0.75 Al₂ O₃ :1.0 P₂ O₅ :0.75 H₂ SO₄ :56 H₂ O.

An aliquot of this final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 200° C. under autogeneous pressure for 168 hours. The solid reaction product (which was determined by the analyses described below to be principally GaAPO-17 was recovered by centrifugation, washed with water and dried in air at ambient temperature.

A sample of this solid reaction product was analyzed and the following chemical analysis obtained:

    ______________________________________                                         Component     Weight percent                                                   ______________________________________                                         Carbon        14.6                                                             Nitrogen      2.1                                                              Ga.sub.2 O.sub.3                                                                             9.2                                                              Al.sub.2 O.sub.3                                                                             25.2                                                             P.sub.2 O.sub.5                                                                              41.1                                                             LOI*          25.9                                                             ______________________________________                                          *LOI indicates loss on ignition.                                         

The above chemical analysis corresponds to a product composition in molar oxide ratios of:

0.60 QN:0.17 Ga₂ O₃ :0.85 Al₂ O₃ :1.0 P₂ O₅ :1.3 H₂ O

which corresponds to an empirical chemical composition, on an anhydrous basis of:

0.15 QN:(Ga₀.08 Al₀.42 P₀.49)O₂

so that the product contained gallium, aluminum and phosphorus in amounts within the hexagonal compositional area defined by points A, B, C, D, E and F of FIG. 1.

The X-ray powder diffraction pattern of the major component of the product, as synthesized, was characterized by the data in the following Table EA:

                  TABLE EA                                                         ______________________________________                                         (GaAPO-17)                                                                                         Relative Intensity                                         2θ    d(Å)                                                                               100 × I/I.sub.o                                      ______________________________________                                         7.7         11.57   100                                                        9.7         9.14    41                                                         11.9        7.46     4                                                         13.3        6.65    39                                                         14.2        6.26    18                                                         15.4        5.75    61                                                         16.5        5.37    28                                                         17.9        4.96    22                                                         19.5        4.55    68                                                         20.5        4.34    82                                                         21.3        4.17    38                                                         22.4        3.97     8                                                         23.2        3.83    24                                                         23.8        3.75    32                                                         25.2        3.54    64                                                         26.9        3.31    31                                                         27.3        3.27    14                                                         28.0        3.19     4                                                         28.6        3.12    20                                                         30.6        2.93    11                                                         31.2        2.87    25                                                         31.7         2.819  56                                                         33.5         2.676  14                                                         35.9         2.504   7                                                         36.3         2.476   6                                                         39.7         2.268   8                                                         43.6         2.078   9                                                         45.7         1.986   4                                                         46.5         1.952   4                                                         47.8         1.904   3                                                         48.7         1.871   3                                                         49.1         1.857   9                                                         49.7         1.835   8                                                         51.7         1.768   8                                                         ______________________________________                                    

Electron microprobe spot analysis of clean crystals in the product indicated the following approximate composition:

    Ga.sub.0.11 Al.sub.0.39 P.sub.0.50

thus indicating that the product contained gallium, aluminum and phosphorus in amounts with the hexagonal compositional area defined by points A, B, C, D, E and F of FIG. 1.

b) Another aliquot of the reaction mixture was digested in the same manner except that the digestion was continued for only 72 hours. The X-ray powder diffraction pattern of the resultant product was essentially the same as in Table EA above.

c) A sample of the product produced in part (b) was utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus. Before being used in the adsorption tests, the sample was activated by heating to 450° C. for 7 hours in vacuum, whereupon a weight loss of 12.7 percent was observed. Before each new adsorbate, the sample was reactivated by heating to 350° C. in vacuum. The following data were generated in the adsorption studies:

    ______________________________________                                                  Kinetic    Pressure         Wt. %                                     Adsorbate                                                                               Diameter (Å)                                                                          (Torr)   Temp, °C.                                                                       Adsorbed*                                 ______________________________________                                         O.sub.2  3.46       102      -183    7.9                                       O.sub.2  3.46       698      -183    9.9                                       n-Hexane 4.3        44       23      3.4                                       iso-Butane                                                                              5.0        705      22      0.8                                       H.sub.2 O                                                                               2.65       4.6      23      10.2                                      H.sub.2 O                                                                               2.65       19.6     23      18.2                                      ______________________________________                                    

From the above data, the pore size of the calcined product was determined to be greater than about 4.3 Å, as shown by the adsorption of n-hexane (kinetic diameter of 4.3 Å) but less than about 5.0 Å, as shown by the negligable adsorption of iso-butane (kinetic diameter of 5.0 Å).

EXAMPLE 6 (PREPARATION OF GAAPO-17)

a) To prepare GaAPO-17, a reaction mixture was formed by dissolving 5.6 grams of quinuclidine (QN) in 19.6 grams of water, and stirring in 2.7 grams of gallium(III) hydroxide (86.4% Ga₂ O₃, 13.5% H₂ O). There was then added to the reaction mixture a solution formed by mixing 11.5 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄) with 11.6 grams of water, and the resultant mixture was stirred until homogeneous. To this homogeneous solution were added 5.1 grams of hydrated aluminum oxide in the form of a pseudo-boehmite phase comprising 75.1 wt. percent of Al₂ O₃ and 24.9 wt. percent H₂ O, and the resultant solution stirred until homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

1.0 QN:0.25 Ga₂ O₃ :0.75 Al₂ O₃ :1.0 P₂ O₅ :41 H₂ O.

This final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 200° C. under autogeneous pressure for 121 hours. The solid reaction product (which was determined by the analyses described below to be principally GaAPO-17) was recovered by centrifugation, washed with water and dried in air at ambient temperature.

The X-ray powder diffraction pattern of the major component of the product, as synthesized, was essentially that set forth in Table EA above.

Electron microprobe spot analysis of clean crystals in the product indicated the following approximate composition:

    Ga.sub.0.05 Al.sub.0.45 P.sub.0.50

thus indicating that the product contained gallium, aluminum and phosphorus in amounts within the hexagonal compositional area defined by points A, B, C, D, E and F of FIG. 1.

Both the GaAPO-17 compositions prepared in Examples 5 and 6 had similar X-ray powder diffraction patterns. The following general Table EB summarizes the X-ray powder diffraction lines which were obtained from these and other specimens of GaAPO-17; the least intense lines were not obtained from all specimens.

                  TABLE EB                                                         ______________________________________                                         (GaAPO-17)                                                                                           Relative Intensity                                       2θ    d(Å)  100 × I/I.sub.o                                    ______________________________________                                         7.6-7.8     11.57-11.27                                                                               87-100                                                  9.7-9.9     9.14-8.95 30-45                                                    11.9-12.0   7.46-7.38 2-5                                                      13.3-13.5   6.65-6.57 32-39                                                    14.2-14.3   6.26-6.18 10-22                                                    15.4-15.6   5.75-5.69 46-65                                                    16.5-16.7   5.37-5.32 24-28                                                    17.9-18.1   4.96-4.91 18-29                                                    19.5-19.7   4.55-4.52  47-100                                                  20.5-20.6   4.34-4.31 62-83                                                    21.3-21.5   4.17-4.14 33-46                                                    22.4-22.6   3.97-3.94  7-11                                                    23.2-23.4   3.83-3.81 18-27                                                    23.7-23.9   3.75-3.73 28-34                                                    25.2-25.3   3.54-3.51  37-100                                                  26.9-27.0   3.31-3.30 23-33                                                    27.3-27.5   3.27-3.25 13-16                                                    28.0-28.2   3.19-3.17 4-6                                                      28.6-28.8   3.12-3.10 13-29                                                    30.6-30.7   2.93-2.91 10-12                                                    31.2-31.3   2.870-2.857                                                                              24-26                                                    31.7-31.9   2.819-2.806                                                                              54-61                                                    33.5-33.6   2.676-2.664                                                                              13-18                                                    35.9-36.0   2.504-2.493                                                                               7-10                                                    36.3-36.4   2.476-2.466                                                                               6-12                                                    36.7-36.8   2.446-2.441                                                                              5-8                                                      37.2        2.415     4                                                        39.7-39.9   2.268-2.260                                                                              7-8                                                      43.6-43.7   2.078- 2.071                                                                              6-13                                                    45.7-45.9   1.986-1.976                                                                              4-7                                                      46.4-46.7   1.955-1.944                                                                              4-5                                                      47.8-47.9   1.904-1.897                                                                              3-5                                                      48.7-48.8   1.871-1.865                                                                              2-6                                                      49.1-49.3   1.857-1.848                                                                               5-20                                                    49.7-49.8   1.835-1.830                                                                               8-10                                                    50.4        1.810     2-3                                                      51.2        1.785     3                                                        51.7-52.2   1.768-1.754                                                                               7-11                                                    54.3-54.4   1.689-1.687                                                                              8                                                        ______________________________________                                    

EXAMPLE 7 (PREPARATION OF GAAPO-13)

a) GaAPO-31 is prepared from a reaction mixture having a composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture, of:

1.0-2.0 DPA:0.05-0.2 Ga₂ O₃ :0.5-1.0 Al₂ O₃ :0.5-1.0 P₂ O₅ :40-100 H₂ O

where "DPA" denotes di-n-propylamine.

The reaction mixture is seeded with crystals of AlPO₄ -31 (U.S. Pat. No. 4,310,440) and digested by placing the reaction mixture in a sealed stainless steel pressure vessel and heating it at an effective temperature and for an effective time until crystals of the GaAPO-31 product are obtained. Solids are then recovered by filtration, washed with water and dried in air at room temperature.

The GaAPO-31 product's chemical analysis shows the GaAPO-31 product contains gallium, aluminum and phosphorus in amounts within the hexagonal compositional area defined by points A, B, C, E and F of FIG. 1.

The X-ray powder diffraction pattern of a GaAPO-31 product is characterized by the following data:

    ______________________________________                                         2θ    d(Å)  Relative Intensity                                       ______________________________________                                         8.5-8.6     10.40-10.28                                                                              m-s                                                      20.2-20.3   4.40-4.37 m                                                        21.9-22.1   4.06-4.02 w-m                                                      22.6-22.7   3.93-3.92 vs                                                       31.7-31.8   2.823-2.814                                                                              w-m                                                      ______________________________________                                    

b) The X-ray powder diffraction pattern for a calcined GaAPO-31 is also characterized by the X-ray pattern of part a).

c) When the calcined GaAPO-31 of part (b) is utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus the measurements are made on a sample after activation at 350° C. in vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                  Kinetic    Pressure         Wt. %                                     Adsorbate                                                                               Diameter(Å)                                                                           (Torr)   Temp, °C.                                                                       Adsorbed*                                 ______________________________________                                         O.sub.2  3.46       100      -183    4                                         O.sub.2  3.46       750      -183    6                                         Cyclohexane                                                                             6.0         90      24      3                                         Neopentane                                                                              6.2        700      24      3                                         H.sub.2 O                                                                               2.65       4.3      24      3                                         H.sub.2 O                                                                               2.65        20      24      10                                        ______________________________________                                          *typical amount adsorbed                                                 

The pore diameter of GaAPO-31 is greater than about 6.2 Å.

EXAMPLE 8 (PREPARATION OF GAAPO-34)

a) GaAPO-34 is prepared from a reaction mixture having a composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture, of:

1.0-2.0 TEAOH:0.05-0.2 Ga₂ O₃ :0.5-1.0 Al₂ O₃ :0.5-1.0 P₂ O₅ : 40-100 H₂ O

where "TEAOH" denotes tetraethylammonium hydroxide.

The reaction mixture is digested by placing the reaction mixture in a sealed stainless steel pressure vessel and heating it at an effective temperature and for an effective time until crystals of the GaAPO-34 product are obtained. Solids are then recovered by filtration, washed with water and dried in air at room temperature.

The GaAPO-34 product's chemical analysis shows the GaAPO-34 product contains gallium, aluminum and phosphorus in amounts within the hexagonal compositional area defined by points A, B, C, E and F of FIG. 1.

The X-ray powder diffraction pattern of a GaAPO-34 product is characterized by the following data:

    ______________________________________                                         2θ     d(Å) Relative Intensity                                       ______________________________________                                          9.4-9.65    9.41-9.17                                                                                s-vs                                                    15.9-16.2    5.57-5.47                                                                               vw-m                                                     17.85-18.4   4.97-4.82                                                                               w-s                                                      20.3-20.9    4.37-4.25                                                                                 m-vs                                                   24.95-25.4   3.57-3.51                                                                               vw-s                                                     30.3-30.8    2.95-2.90                                                                               w-s                                                      ______________________________________                                    

b) The X ray powder diffraction pattern for a calcined GaAPO-34 is also characterized by the X-ray pattern of part a).

c) When the calcined GaAPO-34 of part (b) is utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus the measurements are made on a sample after activation at 350° C. in vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                  Kinetic    Pressure         Wt. %                                     Adsorbate                                                                               Diameter(Å)                                                                           (Torr)   Temp, °C.                                                                       Adsorbed*                                 ______________________________________                                         O.sub.2  3.46       100      -183    13                                        O.sub.2  3.46       750      -183    18                                        n-Hexane 4.3        100      24       6                                        H.sub.2 O                                                                               2.65       4.3      24      15                                        H.sub.2 O                                                                               2.65        20      24      21                                        ______________________________________                                          *typical amount adsorbed                                                 

The pore diameter of GaAPO-34 is about 4.3 Å.

EXAMPLE 9 (PREPARATION OF GAAPO-44)

a GaAPO-44 is prepared from a reaction mixture having a composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture, of:

1.0-2.0 CHA: 0.05-0.2 Ga₂ O₃ :0.5-1.0 Al₂ O₃ :0.5-1.0 P₂ O₅ :40-100 H₂ O

where "CHA" denotes cyclohexylamine.

The reaction mixture is digested by placing the reaction mixture in a sealed stainless steel pressure vessel and heating it at an effective temperature and for an effective time until crystals of the GaAPO-44 product are obtained. Solids are then recovered by filtration, washed with water and dried in air at room temperature.

The GaAPO-44 product's chemical analysis shows the GaAPO-44 product contains gallium, aluminum and phosphorus in amounts within the hexagonal compositional area defined by points A, B, C, E and F of FIG. 1.

The X-ray powder diffraction pattern of a GaAPO-44 product is characterized by the following data:

    ______________________________________                                         2θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.4-9.55     9.41-9.26 vs                                                      13.0-13.1    6.81-6.76 w-m                                                     16.0-16.2    5.54-5.47 w-m                                                     20.6-20.85   4.31-4.26 s-vs                                                    24.3-24.4    3.66-3.65 w-vs                                                    30.7-30.95   2.912-2.889                                                                              w-s                                                     ______________________________________                                    

b) When the calcined GaAPO-44 is utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus the measurements are made on a sample after activation at 350° C. in vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                  Kinetic    Pressure         Wt. %                                     Adsorbate                                                                               Diameter(Å)                                                                           (Torr)   Temp, °C.                                                                       Adsorbed*                                 ______________________________________                                         O.sub.2  3.46       100      -183    13                                        O.sub.2  3.46       750      -183    16                                        n-Hexane 4.3        100      24       2                                        H.sub.2 O                                                                               2.65       4.3      24      15                                        H.sub.2 O                                                                               2.65        20      24       7                                        ______________________________________                                          *typical amount adsorbed                                                 

The pore diameter of GaAPO-44 is about 4.3 Å.

EXAMPLE 10 (PREPARATION OF GAAPO-14)

a) To prepare GaAPO-14, a reaction mixture was formed by combining 7.7 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄) with a solution of 18.1 grams of tetramethylammonium hydroxide pentahydrate (TMAOH.5H₂ O) in 9.8 grams of water, and adding to the resultant mixture a solution prepared by dissolving 5.4 grams of gallium(III) sulfate hydrate (Ga₂ (SO₄)₃.12.2H₂ O) in 12.2 grams of water. To the resultant mixture were added 3.4 grams of hydrated aluminum oxide in the form of a pseudo-boehmite phase comprising 75.1 wt. percent of Al₂ O₃ and 24.9 wt. percent H₂ O, and resultant mixture was stirred until it was homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

3.0 TMAOH:0.25 Ga₂ O₃ :0.75 Al₂ O₃ :1.0 P₂ O₅ :0.75 H₂ SO₄ :60 H₂ O.

An aliquot of this final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 200° C. under autogeneous pressure for 144 hours. The solid reaction product (which was determined by the analyses described below to be principally GaAPO-14) was recovered by centrifugation, washed with water and dried in air at ambient temperature.

The X-ray powder diffraction pattern of the major component of the product, as synthesized, was characterized by the data in the following Table CA:

                  TABLE CA                                                         ______________________________________                                         (GaAPO-14)                                                                                         Relative Intensity                                         2θ    d(Å)                                                                               100 × I/I.sub.o                                      ______________________________________                                          9.0        9.8     100                                                        10.9        8.11    2                                                          12.9        6.86    14                                                         15.7        5.64    21                                                         17.7        5.01    4                                                          18.0        4.93    6                                                          21.9        4.06    3                                                          22.1        4.02    4                                                          22.3        3.99    4                                                          22.5        3.95    5                                                          26.0        3.43    3                                                          26.1        3.41    3                                                          27.1        3.29    7                                                          30.0        2.98    4                                                          30.2        2.96    2                                                          36.4         2.468  2                                                          37.7         2.386  2                                                          ______________________________________                                    

b) A sample of the product produced in part (a) was utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus. Before being used in the adsorption tests, the sample was activated by heating to 450° C. for 3 hours in vacuum, whereupon a weight loss of 13.0 percent was observed. Before each new adsorbate, the sample was reactivated by heating to 350° C. in vacuum. The following data were generated in the adsorption studies:

    ______________________________________                                                 Kinetic     Pressure          Wt. %                                    Adsorbate                                                                              Diameter (Å)                                                                           (Torr)   Temp, °C.                                                                        Adsorbed                                 ______________________________________                                         O.sub.2 3.46        102      -183     5.7                                      O.sub.2 3.46        698      -183     7.3                                      n-Hexane                                                                               4.3          44      23       0.2                                      H.sub.2 O                                                                              2.65         4.6     23       15.5                                     H.sub.2 O                                                                              2.65        19.6     23       19.8                                     ______________________________________                                    

From the above data, the pore size of the calcined product was determined to be greater than about 3.46 Å, as shown by the adsorption of oxygen (kinetic diameter of 3.46 Å) but less than about 4.3 Å, as shown by the negligable adsorption of n-hexane (kinetic diameter of 4.3 Å).

EXAMPLE 11 (PREPARATION OF GAAPO-14)

a) To prepare GaAPO-14, 3.2 grams of gallium(III) hydroxide (86.4 wt. percent Ga₂ O₃, 13.6 wt. percent H₂ O) was stirred in a solution of 10.9 grams of tetramethylammonium hydroxide pentahydrate (TMAOH.5H₂ O) in 15.5 grams of water using a magnetic stir-bar for 21 hours in a closed plastic bottle to produce a homogeneous solution. Separately, 13.8 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄) were added to 15.0 grams of water and then there were added to the resultant solution 6.1 grams of hydrated aluminum oxide in the form of a pseudo-boehmite phase comprising 75.1 wt. percent of Al₂ O₃ and 24.9 wt. percent H₂ O. The gallium-containing solution was added to the resultant mixture, which was stirred until it was homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

1.0 TMAOH:0.25 Ga₂ O₃ :0.75 Al₂ O₃ :1.0 P₂ O₅ :40 H₂ O.

This final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 200° C. under autogeneous pressure for 94 hours. The solid reaction product was separated by centrifugation into an easily settled fraction (which was determined by the analyses described below to be principally GaAPO-14) and a smaller, difficultly settled fraction; both fractions were washed with water and dried in air at ambient temperature. Most of the easily settled fraction of the dry solids were passed through a 325 U.S. mesh screen. The X-ray powder diffraction pattern of the easily settled fraction of the product, as synthesized, was essentially identical to that described in Table CA above, but showed indications of a minor crystalline impurity.

A sample of this solid reaction product was analyzed and the following chemical analysis obtained:

    ______________________________________                                         Component     Weight percent                                                   ______________________________________                                         Carbon         6.9                                                             Nitrogen       2.0                                                             Ga.sub.2 O.sub.3                                                                             18.7                                                             Al.sub.2 O.sub.3                                                                             21.7                                                             P.sub.2 O.sub.5                                                                              42.7                                                             LOI*          16.5                                                             ______________________________________                                          *LOI indicates loss on ignition.                                         

The above chemical analysis corresponds to a product composition in molar oxide ratios of:

0.48 TMAOH:0.33 Ga₂ O₃ 0.71 Al₂ O₃ :1.0 P₂ O₅ :0.63 H₂ O

which corresponds to an empirical chemical composition, on an anhydrous basis of:

    0.12 TMAOH:(Ga.sub.0.16 Al.sub.0.35 P.sub.0.49)O.sub.2

so that the product contained gallium, aluminum and phosphorus in amounts within the hexagonal compositional area defined by points A, B, C, D, E and F of FIG. 1.

A further sample of the solid reaction product was subjected to thermogravimetric analysis by heating it in flowing air while raising its temperature 5° C. per minute. The results of this thermogravimetric analysis were consistent with the chemical analysis given above; a weight loss corresponding to most of the expected 3.5 wt. percent of water being observed by 250° C., while the remaining part of the loss on ignition due to the TMAOH was observed to occur rapidly between 425° and 525° C.

EXAMPLE 12 (PREPARATION OF GAAPO-14)

a) To prepare GaAPO-14, a reaction mixture was formed by combining 9.2 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄) with 10.0 grams of water, then adding to the resultant solution 4.1 grams of hydrated aluminum oxide in the form of a pseudo-boehmite phase comprising 75.1 wt. percent of Al₂ O₃ and 24.9 wt. percent H₂ O. To the resultant mixture was added a suspension of 2.2 grams of gallium(III) hydroxide (86.4% Ga₂ O₃, 13.5% H₂ O) in a solution of 7.2 grams of tetramethylammonium hydroxide pentahydrate (TMAOH.5H₂ O) in 10.3 grams of water, and the resultant mixture was stirred vigorously until it was homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

1.0 TMAOH:0.25 Ga₂ O₃ :0.75 Al₂ O₃ :1.0 P₂ O₅ :40 H₂ O.

An aliquot of this final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 200° C. under autogeneous pressure for 78 hours. The solid reaction product (which was determined by the analyses described below to be principally GaAPO-14 but contained significant amounts of impurities, including the initial gallium hydroxide reagent) was recovered by centrifugation, washed with water and dried in air at 100° C.

The X-ray powder diffraction pattern of the major component of the product, as synthesized, was essentially that set forth in Table CA.

Scanning electron microscopy of the solid product showed numerous crystals with a morphology corresponding to that expected for GaAPO-14. Electron microprobe spot analysis of these crystals indicated the following approximate composition:

    Ga.sub.0.07 Al.sub.0.31 P.sub.0.62

thus indicating that the product contained gallium, aluminum and phosphorus in amounts within the hexagonal compositional area defined by points A, B, C, D, E and F of FIG. 1.

b) Another aliquot of the reaction mixture was digested in the same manner except that the digestion was conducted at 150° C. for 169 hours. The X-ray powder diffraction pattern of the resultant product, as synthesized, was essentially that set forth in Table CA above.

A sample of the resultant product was calcined in air by heating it to 100° C. for 2 hours, then raising its temperature from 100° C. to 400° C. at 75° C. per hour, and finally holding it at 400° C. for 25 hours. The calcined product was impure, but the x-ray powder diffraction pattern of the major component of the calcined product was characterized by the data in the following Table CB:

                  TABLE CB                                                         ______________________________________                                         (GaAPO-14)                                                                                         Relative Intensity                                         2θ    d (Å)                                                                              100 × I/I.sub.o                                      ______________________________________                                          9.0        9.8     100                                                        11.3        7.85    5                                                          13.3        6.67    17                                                         15.7        5.65    5                                                          18.0        4.92    44                                                         19.1        4.65    11                                                         21.2        4.18    4                                                          22.1        4.02    6                                                          22.3        3.98    4                                                          22.8        3.89    9                                                          26.6        3.35    10                                                         27.2        3.28    24                                                         28.8        3.10    4                                                          29.2        3.06    6                                                          29.7        3.01    11                                                         30.2        2.96    9                                                          30.9        2.89    14                                                         32.0         2.796  7                                                          33.9         2.648  6                                                          34.0         2.635  7                                                          35.2         2.552  8                                                          36.2         2.484  9                                                          ______________________________________                                    

All the GaAPO-14 compositions prepared in examples 10-12 had similar power X-ray diffraction patterns. The following general Table CC summarizes the X-ray power diffraction lines which were obtained from the various specimens of GaAPO-14; the least intense lines were not obtained from every specimen.

                  TABLE CC                                                         ______________________________________                                         (GaAPO-14)                                                                                           Relative Intensity                                       2θ    d (Å) 100 × I/I.sub.o                                    ______________________________________                                         8.9-9.1     9.89-9.77 100                                                      9.3-9.4     9.53-9.48 1-5                                                      10.9-11.0   8.14-8.01 2-5                                                      11.1-11.3   7.97-7.85 1-9                                                      12.9-13.3   6.86-6.67  6-24                                                    14.5-14.8   6.09-6.00 1-3                                                      15.7-15.8   5.66-5.61  5-35                                                    17.7-18.1   5.02-4.91  4-44                                                    19.1        4.65       11                                                      21.2-21.4   4.18-4.15 1-4                                                      21.9-22.0   4.06-4.05 3-5                                                      22.0-22.1   4.03-4.02 4-6                                                      22.2-22.8   4.00-3.89  4-13                                                    25.9-26.1   3.44-3.41  3-10                                                    26.1-26.6   3.41-3.35  3-13                                                    27.1-27.2   3.30-3.28  3-24                                                    28.7-28.8   3.11-3.10 1-4                                                      28.9-29.0   3.09-3.08 1-5                                                      29.2-29.3   3.06-3.05 1-6                                                      29.6-30.2   3.02-2.96  1-11                                                    30.2-30.9   2.96-2.89  2-14                                                    33.4-34.0   2.682-2.635                                                                              1-7                                                      35.2-35.5   2.552-2.532                                                                              1-8                                                      36.2-36.5   2.484-2.459                                                                              1-9                                                      37.7-37.9   2.387-2.377                                                                              2-4                                                      38.5-38.7   2.337-2.329                                                                              1-3                                                      ______________________________________                                    

EXAMPLE 13 (PREPARATION OF GAAPO-16)

a) To prepare GaAPO-16, a reaction mixture was formed by dissolving 5.6 grams of quinuclidine (QN) in 19.6 grams of water, and stirring in 2.7 grams of gallium(III) hydroxide (86.4% Ga₂ O₃, 13.5% H₂ O). There was then added to the reaction mixture a solution formed by mixing 11.5 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄) with 11.6 grams of water and the resultant mixture was stirred until homogeneous. To this homogeneous solution were added 5.1 grams of hydrated aluminum oxide in the form of a pseudo-boehmite phase comprising 75.1 wt. percent of Al₂ O₃ and 24.9 wt. percent H₂ O, and the resultant solution was stirred until homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

1.0 QN:0.25 Ga₂ O₃ :0.75 Al₂ O₃ :1.0 P₂ O₅ :41 H₂ O.

This final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 200° C. under autogeneous pressure for 48 hours. The solid reaction product was separated by centrifugation into an easily settled fraction and a smaller, difficultly settled fraction (which was determined by the analyses described below to be principally GaAPO-16); both fractions were washed with water and dried in air at ambient temperature.

The X-ray powder diffraction pattern of the major component of the difficultly settled fraction of the product, as synthesized, was characterized by the data in the following Table DA:

                  TABLE DA                                                         ______________________________________                                         (GaAPO-16)                                                                                         Relative Intensity                                         2θ    d (Å)                                                                              100 × I/I.sub.o                                      ______________________________________                                         11.5        7.67    73                                                         18.9        4.7     57                                                         22.1        4.02    100                                                        23.0        3.86    10                                                         26.7        3.33    24                                                         29.2        3.06    10                                                         30.0        2.98    28                                                         32.9         2.721   4                                                         34.9         2.568   5                                                         38.2         2.357  10                                                         48.7         1.871   7                                                         ______________________________________                                    

Other specimens of GaAPO-16 prepared in a similar manner had similar X-ray power diffraction patterns. The following general Table DB summarizes the X-ray powder diffraction lines which were obtained from the various specimens of GaAPO-16; the least intense lines were not obtained from every specimen.

                  TABLE DB                                                         ______________________________________                                         (GaAPO-16)                                                                                           Relative Instensity                                      2θ    d(Å)  100 × I/I.sub.o                                    ______________________________________                                         11.5        7.69      64-75                                                    18.8-18.9   4.72-4.70 47-57                                                    22.1        4.02-4.03 100                                                      23.0-23.1   3.86-3.84 10-14                                                    26.7-26.8   3.34-3.33 24-36                                                    29.2-29.3   3.06-3.05 10-14                                                    29.9-30.0   2.987-2.982                                                                              26-28                                                    32.9        2.72      4-6                                                      34.9        2.57      5-7                                                      38.1-38.2   2.361-2.354                                                                               8-10                                                    48.6-48.8   1.873-1.867                                                                              7-8                                                      ______________________________________                                    

EXAMPLE 14 (PREPARATION OF GAAPO-18)

a) To prepare GaAPO-18, 2.2 grams of gallium(III) hydroxide (86.4 wt. percent Ga₂ O₃, 13.5 wt. percent H₂ O) was stirred in 29.4 grams of 40 wt. percent aqueous tetraethylammonium hydroxide (TEAOH) for a prolonged period to produce a homogeneous solution. To the resultant solution were added 5.8 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄), and to the resultant mixture was added to a solution of 6.1 grams of aluminum isopropoxide (Al(OCH₃ H₇)₃) in 7.6 grams of water. The resultant mixture was stirred until it was homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

3.2 TEAOH:0.4 Ga₂ O₃ :0.6 Al₂ O₃ :1.0 P₂ O₅ :60 H₂ O:3.6 isopropanol.

An aliquot of this final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 200° C. under autogeneous pressure for 144 hours. The solid reaction product (which was determined by the analyses described below to be principally GaAPO-18) was separated by centrifugation, washed with water and dried in air at ambient temperature.

The X-ray powder diffraction pattern of the product, as synthesized, was characterized by the data in the following Table FA:

                  TABLE FA                                                         ______________________________________                                         (GaAPO-18)                                                                                         Relative Intensity                                         2θ    d (Å)                                                                              100 × I/I.sub.o                                      ______________________________________                                          9.6        9.16    100                                                        10.5        8.43    3                                                          11.1        8.00    5                                                          14.1        6.30    3                                                          14.8        5.98    3                                                          15.6        5.68    11                                                         16.9        5.24    26                                                         17.0        5.20    25                                                         17.9        4.95    18                                                         20.2        4.40    16                                                         21.1        4.22    17                                                         22.2        4.01    5                                                          24.4        3.65    3                                                          25.0        3.57    5                                                          25.5        3.49    8                                                          26.1        3.41    5                                                          26.8        3.32    5                                                          28.1        3.18    12                                                         30.1         2.967  11                                                         30.9         2.893  4                                                          31.4         2.849  9                                                          32.5         2.756  16                                                         33.5         2.675  3                                                          49.6         1.838  5                                                          ______________________________________                                    

b) Another aliquot of the reaction mixture was digested in the same manner except that the digestion was continued for only 72 hours. The X-ray powder diffraction pattern of the resultant product was essentially the same as in Table FA above.

Scanning electron microscopy of this solid product showed numerous crystals with a morphology corresponding to that expected for GaAPO-18. Electron microprobe analysis of these crystals indicated the following approximate composition:

    Ga.sub.0.08 Al.sub.0.41 P.sub.0.51

thus indicating that the product contained gallium, aluminum and phosphorus in amounts within the hexagonal compositional area defined by points A, B, C, D, E and F of FIG. 1.

c) A sample of the product produced in part (b) was utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus. Before being used in the adsorption tests, the sample was activated by heating to 450° C. for 3 hours in vacuum. Before each new adsorbate, the sample was reactivated by heating to 350° C. in vacuum. The following data were generated in the adsorption studies:

    ______________________________________                                                 Kinetic     Pressure          Wt. %                                    Adsorbate                                                                              Diameter (Å)                                                                           (Torr)   Temp, °C.                                                                        Adsorbed                                 ______________________________________                                         O.sub.2 3.46        102      -183     23.9                                     O.sub.2 3.46        698      -183     27.4                                     n-Hexane                                                                               4.3          44      23        6.2                                     n-Butane                                                                               4.3         758      22        9.7                                     iso-Butane                                                                             5.0         705      22        0.2                                     H.sub.2 O                                                                              2.65         4.6     23       28.8                                     H.sub.2 O                                                                              2.65        19.6     23       35.5                                     ______________________________________                                    

From the above data, the pore size of the calcined product was determined to be greater than about 4.3 Å, as shown by the adsorption of n-butane and n-hexane (kinetic diameter of 4.3 Å) but less than about 5.0 Å, as shown by the negligable adsorption of isobutane (kinetic diameter of 5.0 Å).

d) The sample used in the adsorption tests described in part c) above was analyzed and the following chemical analysis obtained:

    ______________________________________                                         Component     Weight percent                                                   ______________________________________                                         Carbon         1.2                                                             Nitrogen       0.12                                                            Ga.sub.2 O.sub.3                                                                              7.0                                                             Al.sub.2 O.sub.3                                                                             24.9                                                             P.sub.2 O.sub.5                                                                              43.6                                                             LOI*          25.2                                                             ______________________________________                                          *LOI indicates loss on ignition.                                         

The above chemical analysis corresponds to a product composition in molar oxide ratios of:

0.04 TEAOH:0.12 Ga₂ O₃ : 0.80 Al₂ O₃ :1.0 P₂ O₅ :4.2 H₂ O

which corresponds to an empirical chemical composition, on an anhydrous basis of:

    0.01 TEAOH:(Ga.sub.0.06 Al.sub.0.42 P.sub.0.52)O.sub.2

so that the product contained gallium, aluminum and phosphorus in amounts within the hexagonal compositional area defined by points A, B, C, D, E and F of FIG. 1.

The two specimens of GaAPO-18 prepared as described above and other specimens of the same material had similar X-ray powder diffraction patterns. The following general Table FB summarizes the X-ray powder diffraction lines which were obtained from the various specimens of GaAPO-18; the least intense lines were not obtained from every specimen.

                  TABLE FB                                                         ______________________________________                                         (GaAPO-18)                                                                                           Relative Intensity                                       2θ    d(Å)  100 × I/I.sub.o                                    ______________________________________                                          9.5-9.7     9.27-9.14                                                                               100                                                      10.4-10.5   8.48-8.43 3                                                        11.0-11.1   8.07-8.00 3-5                                                      13.2        6.71-6.70 1-5                                                      14.0-14.1   6.31-6.30 3                                                        14.8-14.9   5.98-5.92 3-4                                                      15.5-15.7   5.73-5.64 11-20                                                    16.9        5.25-5.24 25-26                                                    17.0-17.1   5.21-5.19 24-40                                                    17.8-17.9   4.97-4.94  7-19                                                    19.6        4.54-4.52 1-3                                                      20.2        4.40-4.39 13-16                                                    21.0-21.1   4.22      17-27                                                    22.1-22.2   4.02-4.01 5-7                                                      23.9-24.0   3.72-3.71 2-3                                                      24.4        3.65-3.64 3-4                                                      24.9-25.0   3.58-3.57 4-5                                                      25.5        3.49       8-11                                                    26.1-26.2   3.41-3.40 5-6                                                      26.5-26.6   3.36-3.35 3-4                                                      26.8-26.9   3.33-3.31 5                                                        28.0-28.1   3.18-3.17  6-12                                                    30.1        2.967-2.964                                                                              11-12                                                    30.8-30.9   2.899-2.893                                                                              4-7                                                      31.4        2.852-2.846                                                                               9-12                                                    31.8-31.9   2.812-2.808                                                                              2-5                                                      32.5        2.758-2.753                                                                              16                                                       33.4-33.5   2.680-2.674                                                                              3-4                                                      49.5-49.6   1.840-1.838                                                                              5                                                        49.9-50.0   1.826-1.823                                                                              1-3                                                      51.0-51.2   1.790-1.785                                                                              2-3                                                      ______________________________________                                    

EXAMPLE 15 (PREPARATION OF GAAPO-20)

a) The smaller, difficultly-settleable fraction produced in Example 11 above was washed and dried as stated in that Example and subjected to powder X-ray and chemical analyses, which proved it to be GaAPO-20. The X-ray powder diffraction pattern of the product, as synthesized, was characterized by the data in the following Table GA:

                  TABLE GA                                                         ______________________________________                                         (GaAPO-20)                                                                                         Relative Intensity                                         2θ     d(Å)                                                                              100 × I/I.sub.o                                      ______________________________________                                         14.0         6.32   52                                                         19.9         4.47   49                                                         22.2         4.01    5                                                         24.4         3.65   100                                                        28.3         3.16   20                                                         31.7         2.824  12                                                         34.8         2.579  19                                                         37.6         2.389   3                                                         40.4         2.234   4                                                         43.0         2.103   6                                                         47.7         1.907   5                                                         52.3         1.749  10                                                         ______________________________________                                    

The following chemical analysis was obtained:

    ______________________________________                                         Component     Weight percent                                                   ______________________________________                                         Carbon         7.3                                                             Nitrogen       2.0                                                             Ga.sub.2 O.sub.3                                                                             11.7                                                             Al.sub.2 O.sub.3                                                                             25.3                                                             P.sub.2 O.sub.5                                                                              45.2                                                             LOI*          18.2                                                             ______________________________________                                          *LOI indicates loss on ignition.                                         

The above chemical analysis corresponds to a product composition in molar oxide ratios of:

0.48 TMAOH:0.20 Ga₂ O₃ :0.78 Al₂ O₃ :1.0 P₂ O₅ :0.75 H₂ O which corresponds to an empirical chemical composition, on an anhydrous basis of:

    0.12 TMAOH:(Ga.sub.0.10 Al.sub.0.40 P.sub.0.51)O.sub.2

so that the product contained gallium, aluminum and phosphorus in amounts within the hexagonal compositional area defined by points A, B, C, D, E and F of FIG. 1.

b) A sample of the product produced in part (a) was utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus. Before being used in the adsorption tests, the sample was activated by heating to 450° C. for 4.5 hours in vacuum, whereupon a weight loss of 11.1 percent was observed. Before each new adsorbate, the sample was reactivated by heating to 350° C. in vacuum. The following data were generated in the adsorption studies:

    ______________________________________                                                 Kinetic     Pressure          Wt. %                                    Adsorbate                                                                              Diameter (Å)                                                                           (Torr)   Temp, °C.                                                                        Adsorbed                                 ______________________________________                                         O.sub.2 3.46        102      -183     1.5                                      O.sub.2 3.46        698      -183     3.9                                      n-Hexane                                                                               4.3          44      23       1.6                                      n-Butane                                                                               4.3         758      22       1.2                                      H.sub.2 O                                                                              2.65         4.6     23       10.5                                     H.sub.2 O                                                                              2.65        13.5     23       13.3                                     ______________________________________                                    

From the above data, the pore size of the calcined product was determined to be greater than about 2.65 Å, as shown by the adsorption of water (kinetic diameter of 2.65 Å) but less than about 3.46 Å, as shown by the low adsorption of oxygen (kinetic diameter of 3.46 Å).

c) A further specimen of the same GaAPO-20 product was produced in the same way as in Example 11 above, except that a fresh batch of the reaction mixture was used and the digestion was continued for only 78 hours. Although the resultant solid product was impure, the presence of GaAPO-20 was verified by detection of the powder X-ray diffraction pattern set out in Table GA above.

Scanning electron microscopy of this solid product showed numerous crystals with a morphology corresponding to that expected for GaAPO-20. Electron microprobe analysis of these crystals indicated the following approximate composition:

    Ga.sub.0.09 Al.sub.0.32 P.sub.0.59

thus indicating that the product contained gallium, aluminum and phosphorus in amounts within the hexagonal compositional area defined by points A, B, C, D, E and F of FIG. 1.

d) A further aliquot of the reaction mixture prepared in part (c) above was digested in the same way as in Example 11 except that the digestion was conducted at 150° C. for 169 hours. Again, although the resultant solid product was impure, the presence of GaAPO-20 was verified by detection of the powder X-ray diffraction pattern set out in Table GA above. This product was calcined in air by heating at 100° C. for 2 hours, then raising its temperature from 100° C. to 400° C. at 75° C. per hour and finally holding it at 400° C. for 25 hours. The X-ray powder diffraction pattern of the GaAPO-20 fraction of the calcined product was characterized by the data in the following Table GB:

                  TABLE GB                                                         ______________________________________                                         (GaAPO-20)                                                                                         Relative Intensity                                         2θ    d (Å)                                                                              100 × I/I.sub.o                                      ______________________________________                                         14.2        6.25    100                                                        19.9        4.46    41                                                         24.6        3.62    70                                                         28.5        3.13    18                                                         32.0         2.796  21                                                         35.2         2.552  23                                                         ______________________________________                                    

Thus the two specimens of GaAPO-20 prepared as described above had similar powder X-ray diffraction patterns, both including all the d-spacings set out in Table G above.

EXAMPLE 16 (PREPARATION OF GAAPO-26)

a) To prepare GaAPO-26, a reaction mixture was formed by combining 9.2 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄) with 10.7 grams of water, adding to the resultant mixture 4.1 grams of hydrated aluminum oxide in the form of a pseudo-boehmite phase comprising 75.1 wt. percent of Al₂ O₃ and 24.9 wt. percent H₂ O, and stirring the resultant mixture until it was homogeneous. To this homogeneous mixture was added with stirring a solution prepared by dissolving, by prolonged stirring, 2.2 grams of gallium(III) hydroxide (86.4% gallium hydroxide 13.5% water) in 22.1 grams of 40.0 percent aqueous tetraethylammonium hydroxide (TEAOH). The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

1.5 TEAOH:0.25 Ga₂ O₃ :0.75 Al₂ O₃ :1.0 P₂ O₅ :40 H₂ O.

An aliquot of this final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 150° C. under autogeneous pressure for 73 hours. The solid reaction product (which was determined by the analyses described below to be principally GaAPO-26) was recovered by centrifugation, washed with water and dried in air at ambient temperature.

The X-ray powder diffraction pattern of the major component of the product, as synthesized, was characterized by the data in the following Table HA:

                  TABLE HA                                                         ______________________________________                                         (GaAPO-26)                                                                                         Relative Intensity                                         2θ    d (Å)                                                                              100 × I/I.sub.o                                      ______________________________________                                          8.2        10.8    100                                                         9.7        9.1     13                                                         10.5        8.45    19                                                         13.3        6.65    5                                                          14.2        6.22    7                                                          15.2        5.84    22                                                         16.5        5.38    5                                                          17.3        5.13    9                                                          17.7        5.00    17                                                         19.5        4.55    12                                                         21.8        4.07    14                                                         22.5        3.95    25                                                         24.2        3.67    5                                                          24.8        3.59    4                                                          26.9        3.30    19                                                         28.7        3.11    7                                                          29.2        3.06    6                                                          30.0         2.976  5                                                          30.4         2.937  9                                                          31.7         2.823  7                                                          33.7         2.661  7                                                          34.4         2.605  10                                                         34.9         2.570  3                                                          36.7         2.448  5                                                          38.2         2.355  3                                                          45.4         2.000  3                                                          50.6         1.802  3                                                          ______________________________________                                    

Scanning electron microscopy of the solid product showed numerous crystals with a morphology corresponding to that expected for GaAPO-26. Electron microprobe spot analysis of these crystals indicated the following approximate composition:

    Ga.sub.0.22 Al.sub.0.21 P.sub.0.57

thus indicating that the product contained gallium, aluminum and phosphorus in amounts within the hexagonal compositional area defined by points A, B, C, D, E and F of FIG. 1.

The following chemical analysis was obtained:

    ______________________________________                                         Component     Weight percent                                                   ______________________________________                                         Carbon         9.6                                                             Nitrogen       1.25                                                            Ga.sub.2 O.sub.3                                                                             24.0                                                             Al.sub.2 O.sub.3                                                                             21.8                                                             P.sub.2 O.sub.5                                                                              35.1                                                             LOI*          19.6                                                             ______________________________________                                          *LOI indicates loss on ignition.                                         

The above chemical analysis corresponds to a product composition in molar oxide ratios of:

0.40 TEAOH:0.52 Ga₂ O₃ :0.86 Al₂ O₃ :1.0 P₂ O₅ :1.09 H₂ O

which corresponds to an empirical chemical composition, on an anhydrous basis of:

    0.09 TEAOH:(Ga.sub.0.22 Al.sub.0.36 P.sub.0.42)O.sub.2

so that the product contained gallium, aluminum and phosphorus in amounts within the hexagonal compositional area defined by points A, B, C, D, E and F of FIG. 1.

b) A sample of the product produced in part (a) was utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus. Before being used in the adsorption tests, the sample was activated by heating to 450° C. for 4.5 hours in vacuum, whereupon a weight loss of 18.3 percent was observed. Before each new adsorbate, the sample was reactivated by heating to 350° C. in vacuum. The following data were generated in the adsorption studies:

    ______________________________________                                                 Kinetic     Pressure          Wt. %                                    Adsorbate                                                                              Diameter (Å)                                                                           (Torr)   Temp, °C.                                                                        Adsorbed                                 ______________________________________                                         O.sub.2 3.46        102      -183     15.1                                     O.sub.2 3.46        698      -183     19.1                                     n-Hexane                                                                               4.3          44      23        7.1                                     n-Butane                                                                               4.3         758      22        7.7                                     iso-Butane                                                                             5.0         705      22        0.9                                     H.sub.2 O                                                                              2.65          4.6    23       19.8                                     H.sub.2 O                                                                              2.65        13.5     23       23.1                                     ______________________________________                                    

From the above data, the pore size of the calcined product was determined to be greater than about 4.3 Å, as shown by the adsorption of n-hexane and n-butane (kinetic diameter of 4.3 Å) but less than about 5.0 Å, as shown by the negligable adsorption of isobutane (kinetic diameter of 5.0 Å).

EXAMPLE 17 (PREPARATION OF GAAPO-26)

GaAPO-26 was prepared in the same way as GaAPO-5 in Example 1 above, except that the proportions of the reagents were adjusted to produce a reaction mixture having the following composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture:

5.0 TPA:0.60 Ga₂ O₃ :0.40 Al₂ O₃ :1.0 P₂ O₅ :1.8 H₂ SO₄ :50 H₂ O, and that the digestion was conducted on an aliquot of the reaction mixture at 150° C. for 24 hours. The solid reaction product was determined by powder X-ray analysis to be principally GaAPO-26 and, as synthesized, its powder X-ray diffraction pattern was characterized by the data in the following Table HB:

                  TABLE HB                                                         ______________________________________                                         (GaAPO-26)                                                                                         Relative Intensity                                         2θ    d (Å)                                                                              100 × I/I.sub.o                                      ______________________________________                                          8.2        10.74   40                                                          9.8        9.06    7                                                          10.5        8.45    100                                                        14.3        6.20    3                                                          17.3        5.12    3                                                          17.8        4.99    4                                                          19.6        4.53    4                                                          21.9        4.06    6                                                          22.6        3.93    30                                                         26.9        3.32    6                                                          27.1        3.30    4                                                          27.7        3.22    3                                                          30.1         2.971  3                                                          30.5         2.927  4                                                          31.8         2.816  8                                                          33.8         2.652  3                                                          34.5         2.597  3                                                          35.0         2.564  3                                                          ______________________________________                                    

The GaAPO-26 specimens prepared in Examples 16 and 17 and other specimens of the same material prepared in a similar manner had similar X-ray powder diffraction patterns. The following general Table HC summarizes the X-ray powder diffraction lines which were obtained from the various specimens of GaAPO-26; the least intense lines were not obtained from every specimen.

                  TABLE HC                                                         ______________________________________                                         (GaAPO-26)                                                                                           Relative Intensity                                       2θ    d(Å)  100 × I/I.sub.o                                    ______________________________________                                         8.2-8.3     10.8-10.7 11-100                                                   9.6-9.9     9.2-9.0   1-40                                                     10.5-10.6   8.45-8.35 19-100                                                   13.3-13.5   6.65-6.56 1-7                                                      14.2-14.4   6.22-6.13 1-20                                                     14.9-15.2   5.94-5.84 1-27                                                     16.4-16.7   5.40-5.30 1-17                                                     17.3-17.4   5.13-5.10 1-10                                                     17.7-17.8   5.00-4.97 1-22                                                     19.5-19.9   4.55-4.47 1-28                                                     21.8-22.1   4.07-4.01 3-94                                                     22.5-22.7   3.95-3.92 9-54                                                     24.2-24.4   3.67-3.65 1-5                                                      24.8-24.9   3.60-3.58 1-4                                                      26.8-27.0   3.32-3.28 1-22                                                     27.6-27.7   3.23-3.22 1-5                                                      28.6-28.9   3.12-3.09 1-35                                                     29.1-29.4   3.07-3.04 1-23                                                     30.0-30.2   2.976-2.961                                                                              1-9                                                      30.3-30.6   2.949-2.923                                                                              2-21                                                     30.9-31.3   2.893-2.856                                                                              1-13                                                     31.6-31.8   2.828-2.811                                                                              5-23                                                     33.7-33.8   2.661-2.650                                                                              1-7                                                      34.2-34.6   2.621-2.591                                                                              1-10                                                     34.8-35.1   2.578-2.559                                                                              1-4                                                      36.7-36.9   2.448-2.436                                                                              1-5                                                      38.2-38.3   2.357-2.352                                                                              1-3                                                      38.5-38.6   2.338- 2.330                                                                             1-3                                                      45.3-45.5   2.000-1.992                                                                              1-3                                                      50.7-50.8   1.802-1.797                                                                              1-3                                                      ______________________________________                                    

EXAMPLE 18 (PREPARATION OF GAAPO-33)

GaAPO-33 was prepared in the same way as GaAPO-14 in Example 10 above, except that the proportions of the reagents were adjusted to produce a reaction mixture having the following composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture:

3.0 TMAOH:0.25 Ga₂ O₃ :0.75 Al₂ O₃ :0.9 P₂ O₅ :0.75 H₂ SO₄ :55 H₂ O,

and that the digestion was conducted at 200° C. for 72 hours. The solid reaction product was determined by powder X-ray analyses described below to be principally GaAPO-33 and, as synthesized, its powder X-ray diffraction pattern was characterized by the data in the following Table JA:

                  TABLE JA                                                         ______________________________________                                         (GaAPO-33)                                                                                         Relative Intensity                                         2θ    d (Å)                                                                              100 × I/I.sub.o                                      ______________________________________                                          9.4        9.4     12                                                         12.7        6.96    64                                                         15.4        5.76    9                                                          17.1        5.20    16                                                         17.6        5.04    10                                                         18.1        4.90    3                                                          20.7        4.29    14                                                         21.0        4.23    3                                                          22.3        3.99    3                                                          23.0        3.87    5                                                          24.0        3.70    15                                                         26.2        3.40    17                                                         27.4        3.26    100                                                        29.7        3.01    7                                                          31.0         2.888  4                                                          32.1         2.785  5                                                          34.3         2.613  10                                                         38.2         2.359  3                                                          39.1         2.305  3                                                          46.9         1.938  4                                                          48.1         1.892  4                                                          51.9         1.762  3                                                          52.2         1.753  4                                                          52.6         1.740  6                                                          55.2         1.663  3                                                          ______________________________________                                    

The following chemical analysis was obtained:

    ______________________________________                                         Component     Weight percent                                                   ______________________________________                                         Carbon        8.5                                                              Nitrogen      2.2                                                              Ga.sub.2 O.sub.3                                                                             6.1                                                              Al.sub.2 O.sub.3                                                                             32.9                                                             P.sub.2 O.sub.5                                                                              40.4                                                             LOI*          19.5                                                             ______________________________________                                          *LOI indicates loss on ignition.                                         

The above chemical analysis corresponds to a product composition in molar oxide ratios of:

0.55 TMAOH:0.10 Ga₂ O₃ :1.0 Al₂ O₃ :0.88 P₂ O₅ :0.57 H₂ O

which corresponds to an empirical chemical composition, on an anhydrous basis of:

    0.14 TMAOH:(Ga.sub.0.05 Al.sub.0.50 P.sub.0.44)O.sub.2

so that the product contained gallium, aluminum and phosphorus in amounts within the hexagonal compositional area defined by points A, B, C, D, E and F of FIG. 1.

EXAMPLE 19 (PREPARATION OF GAAPO-36)

a) To prepare GaAPO-36, a reaction mixture was formed by combining 6.6 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄) with 6.5 grams of water, adding to the resultant mixture 2.9 grams of hydrated aluminum oxide in the form of a pseudo-boehmite phase comprising 75.1 wt. percent of Al₂ O₃ and 24.9 wt. percent H₂ O, and stirring the resultant mixture until it was homogeneous. To this homogeneous mixture was added with stirring a solution prepared by dissolving 4.6 grams of gallium(III) sulfate hydrate (Ga₂ (SO₄)₃.12.2H₂ O) in 9.2 grams of water. Finally, there were added to the reaction mixture 12.3 grams of tri-n-propylamine (TPA), and the resultant mixture was stirred until homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

3.0 TPA:0.25 Ga₂ O₃ :0.75 Al₂ O₃ :1.0 P₂ O₅ :0.75 H₂ SO₄ :40 H₂ O.

An aliquot of this final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 150° C. under autogeneous pressure for 73 hours. The solid reaction product (which was determined by the analyses described below to be partly GaAPO-5) was recovered by centrifugation, washed with water and dried in air at ambient temperature.

The X-ray powder diffraction pattern of the GaAPO-36 component of the product, as synthesized, was characterized by the data in the following Table NA:

                  TABLE NA                                                         ______________________________________                                         (GaAPO-36)                                                                                         Relative Intensity                                         2θ    d (Å)                                                                              100 × I/I.sub.o                                      ______________________________________                                          7.8        11.3    100                                                         8.1        11.0    89                                                         16.4        5.40    40                                                         19.1        4.64    27                                                         27.6        3.24    13                                                         27.8        3.21    11                                                         ______________________________________                                    

Scanning electron microscopy of the solid product showed crystals with a morphology corresponding to that expected for GaAPO-36. Electron microprobe spot analysis of these crystals indicated the following approximate composition:

    Ga.sub.0.07 Al.sub.0.43 P.sub.0.50

thus indicating that the product contained gallium, aluminum and phosphorus in amounts within the hexagonal compositional area defined by points A, B, C, D, E and F of FIG. 1.

PROCESS APPLICATIONS

The GaAPO compositions of the present invention are, in general, hydrophilic and adsorb water preferentially over common hydrocarbon molecules such as paraffins, olefins and aromatic species, e.g., benzene, xylenes and cumene. Thus the present molecular sieve compositions as a class are useful as desiccants in such adsorption separation/purification processes as natural gas drying, cracked gas drying. Water is also preferentially adsorbed over the so-called permanent gases such as carbon dioxide, nitrogen, oxygen and hydrogen. These GaAPOs are therefore suitably employed in the drying of reformer hydrogen streams and in the drying of oxygen, nitrogen or air prior to liquifaction.

The present GaAPO compositions also exhibit novel surface selectivity characteristics which render them useful as catalyst or catalyst bases in a number of hydrocarbon conversion and oxidative combustion reactions. They can be impregnated or otherwise loaded with catalytically active metals by methods well known in the art (e.g. ion exchange or impregnation) and used, for example, in fabricating catalyst compositions having silica or alumina bases. Of the general class, those species having pores larger than about 4 Å are preferred for catalytic applications.

Among the hydrocarbon conversion reactions catalyzed by GaAPO compositions are cracking, hydrocracking, alkylation for both the aromatic and isoparaffin types, isomerization including xylene isomerization, polymerization, reforming, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydrodecyclization and dehydrocyclization.

Using GaAPO catalyst compositions which contain a hydrogenation promoter such as platinum or palladium, heavy petroleum residual stocks, cyclic stocks and other hydrocrackable charge stocks, can be hydrocracked at temperatures in the range of 400° F. to 825° F. (204° C. to 441° C.) using molar ratios of hydrogen to hydrocarbon in the range of between 2 and 80, pressures between 10 and 3500 p.s.i.g. (0.171 to 24.23 MPa.), and a liquid hourly space velocity (LHSV) of from 0.1 to 20, preferably 1.0 to 10.

The GaAPO catalyst compositions employed in hydrocracking are also suitable for use in reforming processes in which the hydrocarbon feedstocks contact the catalyst at temperatures of from about 700° F. to 1000° F. (371° C. to 538° C.), hydrogen pressures of from 100 to 500 p.s.i.g. (0.791 to 3.448 MPa.), LHSV values in the range of 0.1 to 10 and hydrogen to hydrocarbon molar ratios in the range of 1 to 20, preferably between 4 and 12.

These same catalysts, i.e. those containing hydrogenation promoters, are also useful in hydroisomerization processes in which feedstocks such as normal paraffins are converted to saturated branched chain isomers. Hydroisomerization is carried out at a temperature of from about 200° F. to 600° F. (93° C. to 316° C.), preferably 300° F. to 550° F. (149° C. to 288° C.) with an LHSV value of from about 0.2 to 1.0. Hydrogen (H) is supplied to the reactor in admixture with the hydrocarbon (Hc) feedstock in molar proportions (H/Hc) of between 1 and 5.

At somewhat higher temperatures, i.e. from about 650° F. to 1000° F. (343° C. to 538° C.), preferably 850° F. to 950° F. (454° C. to 510° C.) and usually at somewhat lower pressures within the range of about 15 to 50 p.s.i.g. (205 to 446 KPa.), the same catalyst compositions are used to hydroisomerize normal paraffins. Preferably the paraffin feedstock comprises normal paraffins having a carbon number range of C₇ -C₂₀. Contact time between the feedstock and the catalyst is generally relatively short to avoid undesirable side reactions such as olefin polymerization and paraffin cracking. LHSV values in the range of 0.1 to 10, preferably 1.0 to 6.0 are suitable.

The unique crystal structure of the present GaAPO catalysts and their availability in a form totally void of alkali metal content favor their use in the conversion of alkylaromatic compounds, particularly the catalytic disproportionation of toluene, ethylene, trimethyl benzenes, tetramethyl benzenes and the like. In the disproportionation process, isomerization and transalkylation can also occur. Group VIII noble metal adjuvants alone or in conjunction with Group VI-B metals such as tungsten, molybdenum and chromium are preferably included in the catalyst composition in amounts of from about 3 to 15 weight-% of the overall composition. Extraneous hydrogen can, but need not, be present in the reaction zone which is maintained at a temperature of from about 400 to 750° F. (204 to 399° C.), pressures in the range of 100 to 2000 p.s.i.g. (0.791 to 13.89 MPa.) and LHSV values in the range of 0.1 to 15.

Catalytic cracking processes are preferably carried out with GaAPO compositions using feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residua, etc., with gasoline being the principal desired product. Temperature conditions of 850° to 1100° F. (454° to 593° C.), LHSV values of 0.5 to 10 and pressure conditions of from about 0 to 50 p.s.i.g. (101 to 446 KPa.) are suitable.

Dehydrocyclization reactions employing paraffinic hydrocarbon feedstocks, preferably normal paraffins having more than 6 carbon atoms, to form benzene, xylenes, toluene and the like are carried out using essentially the same reaction conditions as for catalytic cracking. For these reactions it is preferred to use the GaAPO catalyst in conjunction with a Group VIII non-noble metal cation such as cobalt and nickel.

In catalytic dealkylation wherein it is desired to cleave paraffinic side chains from aromatic nuclei without substantially hydrogenating the ring structure, relatively high temperatures in the range of about 800°-1000° F. (427°-538° C.) are employed at moderate hydrogen pressures of about 300-1000 p.s.i.g. (2.17-6.895 MPa.), other conditions being similar to those described above for catalytic hydrocracking. Preferred catalysts are of the same type described above in connection with catalytic dehydrocyclization. Particularly desirable dealkylation reactions contemplated herein include the conversion of methylnaphthalene to naphthalene and toluene and/or xylenes to benzene.

In catalytic hydrofining, the primary objective is to promote the selective hydrodecomposition of organic sulfur and/or nitrogen compounds in the feed, without substantially affecting hydrocarbon molecules therein. For this purpose it is preferred to employ the same general conditions described above for catalytic hydrocracking, and catalysts of the same general nature described in connection with dehydrocyclization operations. Feedstocks include gasoline fractions, kerosenes, jet fuel fractions, diesel fractions, light and heavy gas oils, deasphalted crude oil residua and the like. Any of these may contain up to about 5 weight-percent of sulfur and up to about 3 weight-percent of nitrogen.

Similar conditions can be employed to effect hydrofining, i.e., denitrogenation and desulfurization, of hydrocarbon feeds containing substantial proportions of organonitrogen and organosulfur compounds. It is generally recognized that the presence of substantial amounts of such constituents markedly inhibits the activity of hydrocracking catalysts. Consequently, it is necessary to operate at more extreme conditions when it is desired to obtain the same degree of hydrocracking conversion per pass on a relatively nitrogenous feed than with a feed containing less organonitrogen compounds. Consequently, the conditions under which denitrogenation, desulfurization and/or hydrocracking can be most expeditiously accomplished in any given situation are necessarily determined in view of the characteristics of the feedstocks, in particular the concentration of organonitrogen compounds in the feedstock. As a result of the effect of organonitrogen compounds on the hydrocracking activity of these compositions it is not at all unlikely that the conditions most suitable for denitrogenation of a given feedstock having a relatively high organonitrogen content with minimal hydrocracking, e.g., less than 20 volume percent of fresh feed per pass, might be the same as those preferred for hydrocracking another feedstock having a lower concentration of hydrocracking inhibiting constituents e.g., organonitrogen compounds. Consequently, it has become the practice in this art to establish the conditions under which a certain feed is to be contacted on the basis of preliminary screening tests with the specific catalyst and feedstock.

Isomerization reactions are carried out under conditions similar to those described above for reforming, using somewhat more acidic catalysts. Olefins are preferably isomerized at temperatures of 500°-900° F. (260°-482° C.), while paraffins, naphthenes and alkyl aromatics are isomerized at temperatures of 700°-1000° F. (371°-538° C.). Particularly desirable isomerization contemplated herein include the conversion of n-heptene and/or n-octane to isoheptanes, iso-octanes, butane to iso-butane, methylcyclopentane to cyclohexane, meta-xylene and/or ortho-xylene to paraxylene, 1-butene to 2-butene and/or isobutene, n-hexane to isohexene, cyclohexene to methylcyclopentene etc. The preferred form of the catalyst is a combination of the GaAPO with polyvalent metal compounds (such as sulfides) of metals of Group II-A, Group II-B and rare earth metals. For alkylation and dealkylation processes the GaAPO compositions having pores of at least 5 Å are preferred. When employed for dealkylation of alkyl aromatics, the temperature is usually at least 350° F. (177° C.) and ranges up to a temperature at which substantial cracking of the feedstock or conversion products occurs, generally up to about 700° F. (371° C.). The temperature is preferably at least 450° F. (232° C.) and not greater than the critical temperature of the compound undergoing dealkylation. Pressure conditions are applied to retain at least the aromatic feed in the liquid state. For alkylation the temperature can be as low as 250° F. (121° C.) but is preferably at least 350° F. (177° C.). In the alkylation of benzene, toluene and xylene, the preferred alkylating agents are olefins such as ethylene and propylene.

The following example is provided to further illustrate the use of the GaAPOs of the invention in one of the processes discussed above, but is not intended to be limitative of the possible uses of the GaAPOs.

EXAMPLE 20 (CRACKING TESTS ON GAAPO-26)

GaAPO-b 26 was prepared from a second aliquot of the reaction mixture prepared in Example 17 above by digesting at 150° C. for 122 hours, then isolating the product in the same way as in Example 17. The n-butane cracking activity of the GaAPO-26 product was tested in a bench-scale apparatus, in which the reactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm. in internal diameter. The reactor was loaded with 0.8 gram of the GaAPO-26. The reactor was heated at 500° C. under helium for 2 hours to calcine the sample, then a feedstock comprising a helium/n-butane mixture containing 2 mole percent of n-butane was passed through the reactor at a rate of 50 mL/min. (STP) at 500° C. for 10 minutes. At the end of this period, the reactor effluent was analyzed using conventional gas chromatography techniques. The resultant data showed a pseudo-first-order rate constant (k_(A)) of 0.6. 

We claim:
 1. Crystalline molecular sieves having three-dimensional microporous framework structures of GaO₂, AlO₂ and PO₂ tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Ga.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Ga_(x) Al_(y) P_(z))O₂ and has a value of zero to about 0.3; and "x", "y" and "z" represent the mole fractions of gallium, aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the hexagonal compositional area defined by points, A, B, C, D, E and F of FIG. 1, said crystalline molecular sieves having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of the following Tables A to V:

                  TABLE A                                                          ______________________________________                                         (GaAPO-5)                                                                      2Θ     d(Å)  Relative Intensity                                      ______________________________________                                          7.3-7.65     12.1-11.56                                                                              m-vs                                                    19.5-20.0    4.55-4.44 m-s                                                     20.9-21.3    4.25-4.17 m-vs                                                    22.2-22.7    4.00-3.92 w-vs                                                    25.7-26.2    3.47-3.40 w-m                                                     ______________________________________                                    

                  TABLE B                                                          ______________________________________                                         (GaAPO-11)                                                                     2Θ     d(Å) Relative Intensity                                       ______________________________________                                          9.3-9.65    9.51-9.17                                                                               m-s                                                      20.2-20.6    4.40-4.31                                                                               m-s                                                      20.9-21.3    4.25-4.17                                                                               s-vs                                                     22.0-22.5    4.04-3.95                                                                               m-s                                                      22.5-22.9    3.95-3.92                                                                               m-s                                                      23.0-23.4    3.85-3.80                                                                               m-vs                                                     ______________________________________                                    

                  TABLE C                                                          ______________________________________                                         (GaAPO-14)                                                                     2Θ     d(Å) Relative Intensity                                       ______________________________________                                         8.9-9.1      9.89-9.77                                                                               vs                                                       12.9-13.3    6.86-6.67                                                                               w-m                                                      15.7-15.8    5.66-5.61                                                                               w-m                                                      17.7-18.1    5.02-4.91                                                                               w-m                                                      22.2-22.8    4.00-3.89                                                                               w                                                        27.1-27.2    3.30-3.28                                                                               w                                                        ______________________________________                                    

                  TABLE D                                                          ______________________________________                                         (GaAPO-16)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         11.3-11.6    7.83-7.63 m-vs                                                    18.7-18.9    4.75-4.70 w-s                                                     21.9-22.3    4.06-3.99 m-vs                                                    26.5-27.0    3.363-3.302                                                                              w-m                                                      29.7-30.05  3.008-2.974                                                                              w-m                                                     ______________________________________                                    

                  TABLE E                                                          ______________________________________                                         (GaAPO-17)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.7-7.8      11.5-11.3 vs                                                      13.3-13.5    6.65-6.57 s-vs                                                    15.4-15.6    5.75-5.69 m-vs                                                    19.5-19.7    4.55-4.51 m-vs                                                    20.5-20.6    4.33-4.31 vs                                                      31.7-32.0    2.819-2.797                                                                              w-s                                                     ______________________________________                                    

                  TABLE F                                                          ______________________________________                                         (GaAPO-18)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.5-9.7      9.27-9.14 vs                                                      15.5-15.7    5.73-5.64 w-m                                                     16.9-17.1    5.25-5.19 m                                                       20.15-20.25  4.41-4.39 m                                                       20.95-21.1   4.24-4.22 w-m                                                     31.8-32.5    2.814-2.755                                                                              m                                                       ______________________________________                                    

                  TABLE G                                                          ______________________________________                                         (GaAPO-20)                                                                     2Θ      d(Å) Relative Intensity                                      ______________________________________                                          13.7-14.25   6.46-6.22                                                                               m-vs                                                    19.55-20.0    4.54-4.44                                                                               w-s                                                     24.05-24.6    3.70-3.63                                                                               m-vs                                                    28.3-28.5     3.16-3.13                                                                               w-m                                                     34.8-35.2     2.58-2.55                                                                               w                                                       ______________________________________                                    

                  TABLE H                                                          ______________________________________                                         (GaAPO-26)                                                                     2Θ     d(Å) Relative Intensity                                       ______________________________________                                         8.2-8.3      10.8-10.7                                                                               w-vs                                                     9.6-9.9      9.2-9.0  vw-m                                                     10.5-10.6    8.45-8.35                                                                               w-vs                                                     21.8-22.1    4.07-4.01                                                                               w-vs                                                     22.5-22.7    3.95-3.92                                                                               w-s                                                      28.6-28.9    3.12-3.09                                                                               vw-m                                                     ______________________________________                                    

                  TABLE I                                                          ______________________________________                                         (GaAPO-31)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         8.5-8.6      10.40-10.28                                                                              m-s                                                     20.2-20.3    4.40-4.37 m                                                       21.9-22.1    4.06-4.02 w-m                                                     22.6-22.7    3.93-3.92 vs                                                      31.7-31.8    2.823-2.814                                                                              w-m                                                     ______________________________________                                    

                  TABLE J*                                                         ______________________________________                                         (GaAPO-33)                                                                     2Θ      d(Å) Relative Intensity                                      ______________________________________                                         9.25-9.55     9.56-9.26                                                                               w-m                                                     12.5-12.9     7.08-6.86                                                                               vs                                                      16.9-17.3     5.25-5.13                                                                               w-m                                                     20.45-20.9    4.34-4.25                                                                               w-m                                                     23.85-24.25   3.73-3.67                                                                               w-m                                                     26.05-26.35   3.42-3.38                                                                               w-m                                                     27.3-27.6     3.27-3.23                                                                               vs                                                      ______________________________________                                          *as-synthesized form                                                     

                  TABLE K*                                                         ______________________________________                                         (GaAPO-33)                                                                     2Θ      d(Å) Relative Intensity                                      ______________________________________                                         13.15-13.4    6.73-6.61                                                                               vs                                                      18.05-18.35   4.91-4.83                                                                               m                                                       18.4-18.6     4.82-4.77                                                                               m                                                       26.55-26.7    3.36-3.34                                                                               m                                                       32.0-32.1     2.80-2.79                                                                               m                                                       ______________________________________                                          *calcined form                                                           

                  TABLE L                                                          ______________________________________                                         (GaAPO-34)                                                                     2Θ      d(Å) Relative Intensity                                      ______________________________________                                          9.4-9.65     9.41-9.17                                                                               s-vs                                                    15.9-16.2     5.57-5.47                                                                               vw-m                                                    17.85-18.4    4.97-4.82                                                                               w-s                                                     20.3-20.9     4.37-4.25                                                                               m-vs                                                    24.95-25.4    3.57-3.51                                                                               vw-s                                                    30.3-30.8     2.95-2.90                                                                               w-s                                                     ______________________________________                                    

                  TABLE M                                                          ______________________________________                                         (GaAPO-35)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         10.8-11.1    8.19-7.97 m                                                       17.2-17.4    5.16-5.10 s-vs                                                     21.0-21.25  4.23-4.18 m-s                                                     21.8-22.0    4.08-4.04 vs                                                      31.8-32.2    2.814-2.788                                                                              m                                                       ______________________________________                                    

                  TABLE N                                                          ______________________________________                                         (GaAPO-36)                                                                     2Θ     d(Å) Relative Intensity                                       ______________________________________                                         7.7-7.9      11.5-11.2                                                                               vs                                                       16.2-16.6    5.47-5.34                                                                               w-m                                                      18.9-19.3    4.70-4.60                                                                               m-s                                                      27.4-27.7    3.26-3.22                                                                               w-m                                                      27.7-28.0    3.22-3.19                                                                               w-m                                                      ______________________________________                                    

                  TABLE O                                                          ______________________________________                                         (GaAPO-37)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         6.1-6.3      14.49-14.03                                                                              vs                                                      15.5-15.7    5.72-5.64 w-m                                                     18.5-18.8    4.80-4.72 w-m                                                     23.5-23.7    3.79-3.75 w-m                                                     26.9-27.1    3.31-3.29 w-m                                                     ______________________________________                                    

                  TABLE P                                                          ______________________________________                                         (GaAPO-39)                                                                     2Θ     d(Å) Relative Intensity                                       ______________________________________                                         9.4-9.6      9.41-9.21                                                                               w-m                                                      13.3-13.6    6.66-6.51                                                                               m-vs                                                     18.0-18.4    4.93-4.82                                                                               m                                                        21.2-21.5    4.19-4.13                                                                               m-s                                                      22.5-23.0    3.95-3.87                                                                               s-vs                                                     30.2-30.5    2.96-2.93                                                                               w-m                                                      ______________________________________                                    

                  TABLE Q                                                          ______________________________________                                         (GaAPO-40)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.5-7.7      11.79-11.48                                                                              vw-m                                                    8.0-8.1      11.05-10.94                                                                              s-vs                                                    12.4-12.5    7.14-7.08 w-vs                                                    13.6-13.8    6.51-6.42 m-s                                                     14.0-14.1    6.33-6.28 w-vs                                                    27.8-28.0    3.209-3.187                                                                              w-m                                                     ______________________________________                                    

                  TABLE R                                                          ______________________________________                                         (GaAPO-41)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         13.6-13.8    6.51-6.42 w-m                                                     20.5-20.6    4.33-4.31 w-m                                                     21.1-21.3    4.21-4.17 vs                                                      22.1-22.3    4.02-3.99 m-s                                                     22.8-23.0    3.90-3.86 m                                                       23.1-23.4    3.82-3.80 w-m                                                     25.5-25.9    3.493-3.440                                                                              w-m                                                     ______________________________________                                    

                  TABLE S                                                          ______________________________________                                         (GaAPO-42)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.15-7.4     12.36-11.95                                                                              m-vs                                                    12.5-12.7    7.08-6.97 m-s                                                     21.75-21.9   4.09-4.06 m-s                                                      24.1-24.25  3.69-3.67 vs                                                      27.25-27.4   3.273-3.255                                                                              s                                                       30.05-30.25  2.974-2.955                                                                              m-s                                                     ______________________________________                                    

                  TABLE T                                                          ______________________________________                                         (GaAPO-44)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                          9.4-9.55    9.41-9.26 vs                                                      13.0-13.1    6.81-6.76 w-m                                                     16.0-16.2    5.54-5.47 w-m                                                      20.6-20.85  4.31-4.26 s-vs                                                    24.3-24.4    3.66-3.65 w-vs                                                     30.7-30.95  2.912-2.889                                                                              w-s                                                     ______________________________________                                    

                  TABLE U                                                          ______________________________________                                         (GaAPO-46)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.2-8.1      12.3-10.9 vs                                                      21.2-21.8    4.19-4.08 w-m                                                     22.5-23.0    3.95-3.87 vw-m                                                    26.6-27.2    3.351-3.278                                                                              vw-w                                                    28.5-29.0    3.132-3.079                                                                              vw-w                                                    ______________________________________                                    

                  TABLE V                                                          ______________________________________                                         (GaAPO-47)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.4          9.41      vs                                                      15.9-16.0    5.57-5.54 w-m                                                     20.5-20.6    4.33-4.31 s                                                       24.5-24.7    3.63-3.60 w                                                       25.8-25.9    3.45-3.44 w                                                       30.4-30.5    2.940-2.931                                                                               w.                                                     ______________________________________                                    


2. Crystalline molecular sieves according to claim 1 wherein "z" is not greater than 0.60.
 3. Crystalline molecular sieves according to claim 1 or 2 wherein "m" is not greater than about 0.15.
 4. Crystalline molecular sieves according to claim 1 wherein the mole fractions of gallium, aluminum and phosphorus present as tetrahedral oxides are within the tetragonal compositional area defined by points a, b, c and d of FIG.
 2. 5. Crystalline molecular sieves according to claim 4 wherein the mole fractions of gallium, aluminum and phosphorus present as tetrahedral oxides are within the hexagonal compositional area defined by points e, f, g, h, i and j of FIG.
 2. 6. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table A given in claim
 1. 7. The crystalline molecular sieves of claim 6 wherein the X-ray powder diffraction pattern set forth in Table A contains at least the d-spacings set forth in the following Table AA:

                  TABLE AA                                                         ______________________________________                                         (GaAPO-5)                                                                                          Relative Intensity                                         2θ    d (Å)                                                                              100 × I/I.sub.o                                      ______________________________________                                          7.4        11.9    100                                                        12.9        6.86    10                                                         14.9        5.95    20                                                         19.8        4.48    38                                                         21.0        4.23    48                                                         22.4        3.97    62                                                         24.7        3.60     3                                                         26.0        3.43    24                                                         29.0        3.08    11                                                         30.1        2.97    17                                                         33.7         2.660   3                                                         34.6         2.592  13                                                         37.0         2.430   3                                                         37.7         2.386   9                                                         41.7         2.165   2                                                         42.2         2.141   2                                                         47.8         1.903   
 4.                                                       ______________________________________                                    


8. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table B given in claim
 1. 9. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table C given in claim
 1. 10. The crystalline molecular sieves of claim 9 wherein the X-ray powder diffraction pattern set forth in Table C contains at least the d-spacings set forth in one of the following Tables CA and CB:

                  TABLE CA                                                         ______________________________________                                         (GaAPO-14)                                                                                         Relative Intensity                                         2θ    d(Å)                                                                               100 × I/I.sub.o                                      ______________________________________                                          9.0        9.8     100                                                        10.9        8.11    2                                                          12.9        6.86    14                                                         15.7        5.64    21                                                         17.7        5.01    4                                                          18.0        4.93    6                                                          21.9        4.06    3                                                          22.1        4.02    4                                                          22.3        3.99    4                                                          22.5        3.95    5                                                          26.0        3.43    3                                                          26.1        3.41    3                                                          27.1        3.29    7                                                          30.0        2.98    4                                                          30.2        2.96    2                                                          36.4         2.468  2                                                          37.7         2.386  2                                                          ______________________________________                                    

                  TABLE CB                                                         ______________________________________                                         (GaAPO-14)                                                                                         Relative Intensity                                         2θ    d(Å)                                                                               100 × I/I.sub.o                                      ______________________________________                                          9.0        9.8     100                                                        11.3        7.85    5                                                          13.3        6.67    17                                                         15.7        5.65    5                                                          18.0        4.92    44                                                         19.1        4.65    11                                                         21.2        4.18    4                                                          22.1        4.02    6                                                          22.3        3.98    4                                                          22.8        3.89    9                                                          26.6        3.35    10                                                         27.2        3.28    24                                                         28.8        3.10    4                                                          29.2        3.06    6                                                          29.7        3.01    11                                                         30.2        2.96    9                                                          30.9        2.89    14                                                         32.0         2.796  7                                                          33.9         2.648  6                                                          34.0         2.635  7                                                          35.2         2.552  8                                                          36.2         2.484  
 9.                                                        ______________________________________                                    


11. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table D given in claim
 1. 12. The crystalline molecular sieves of claim 11 wherein the X-ray powder diffraction pattern set forth in Table D contains at least the d-spacings set forth in the following Table DA:

                  TABLE DA                                                         ______________________________________                                         (GaAPO-16)                                                                                          Relative Intensity                                        2Θ     d(Å)                                                                               100 × I/I.sub.o                                     ______________________________________                                         11.5         7.67    73                                                        18.9         4.70    57                                                        22.1         4.02    100                                                       23.0         3.86    10                                                        26.7         3.33    24                                                        29.2         3.06    10                                                        30.0         2.98    28                                                        32.9          2.721   4                                                        34.9          2.568   5                                                        38.2          2.357  10                                                        48.7          1.871   
 7.                                                      ______________________________________                                    


13. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table E given in claim
 1. 14. The crystalline molecular sieves of claim 13 wherein the X-ray powder diffraction pattern set forth in Table E contains at least the d-spacings set forth in the following Table EA:

                  TABLE EA                                                         ______________________________________                                         (GaAPO-17)                                                                                          Relative Intensity                                        2Θ     d(Å)                                                                               100 × I/I.sub.o                                     ______________________________________                                          7.7         11.57   100                                                        9.7         9.14    41                                                        11.9         7.46     4                                                        13.3         6.65    39                                                        14.2         6.26    18                                                        15.4         5.75    61                                                        16.5         5.37    28                                                        17.9         4.96    22                                                        19.5         4.55    68                                                        20.5         4.34    82                                                        21.3         4.17    38                                                        22.4         3.97     8                                                        23.2         3.83    24                                                        23.8         3.75    32                                                        25.2         3.54    64                                                        26.9         3.31    31                                                        27.3         3.27    14                                                        28.0         3.19     4                                                        28.6         3.12    20                                                        30.6         2.93    11                                                        31.2         2.87    25                                                        31.7          2.819  56                                                        33.5          2.676  14                                                        35.9          2.504   7                                                        36.3          2.476   6                                                        39.7          2.268   8                                                        43.6          2.078   9                                                        45.7          1.986   4                                                        46.5          1.952   4                                                        47.8          1.904   3                                                        48.7          1.871   3                                                        49.1          1.857   9                                                        49.7          1.835   8                                                        51.7          1.768   
 8.                                                      ______________________________________                                    


15. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table F given in claim
 1. 16. The crystalline molecular sieves of claim 15 wherein the X-ray powder diffraction pattern set forth in Table F contains at least the d-spacings set forth in the following Table FA:

                  TABLE FA                                                         ______________________________________                                         (GaAPO-18)                                                                                          Relative Intensity                                        2Θ     d(Å)                                                                               100 × I/I.sub.o                                     ______________________________________                                          9.6         9.16    100                                                       10.5         8.43    3                                                         11.1         8.00    5                                                         14.1         6.30    3                                                         14.8         5.98    3                                                         15.6         5.68    11                                                        16.9         5.24    26                                                        17.0         5.20    25                                                        17.9         4.95    18                                                        20.2         4.40    16                                                        21.1         4.22    17                                                        22.2         4.01    5                                                         24.4         3.65    3                                                         25.0         3.57    5                                                         25.5         3.49    8                                                         26.1         3.41    5                                                         26.8         3.32    5                                                         28.1         3.18    12                                                        30.1          2.967  11                                                        30.9          2.893  4                                                         31.4          2.849  9                                                         32.5          2.756  16                                                        33.5          2.675  3                                                         49.6          1.838  
 5.                                                       ______________________________________                                    


17. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table G given in claim
 1. 18. The crystalline molecular sieves of claim 17 wherein the X-ray powder diffraction pattern set forth in Table G contains at least the d-spacings set forth in the following Table GA:

                  TABLE GA                                                         ______________________________________                                         (GaAPO-20)                                                                                          Relative Intensity                                        2Θ     d(Å)                                                                               100 × I/I.sub.o                                     ______________________________________                                         14.0         6.32    52                                                        19.9         4.47    49                                                        22.2         4.01     5                                                        24.4         3.65    100                                                       28.3         3.16    20                                                        31.7         2.824   12                                                        34.8         2.579   19                                                        37.6         2.389    3                                                        40.4         2.234    4                                                        43.0         2.103    6                                                        47.7         1.907    5                                                        52.3         1.749   
 10.                                                      ______________________________________                                    


19. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table H given in claim
 1. 20. The crystalline molecular sieves of claim 19 wherein the X-ray powder diffraction pattern set forth in Table H contains at least the d-spacings set forth in one of the following Tables HA and HB:

                  TABLE HA                                                         ______________________________________                                         (GaAPO-26)                                                                                          Relative Intensity                                        2Θ     d(Å)                                                                               100 × I/I.sub.o                                     ______________________________________                                          8.2         10.8    100                                                        9.7         9.1     13                                                        10.5         8.45    19                                                        13.3         6.65    5                                                         14.2         6.22    7                                                         15.2         5.84    22                                                        16.5         5.38    5                                                         17.3         5.13    9                                                         17.7         5.00    17                                                        19.5         4.55    12                                                        21.8         4.07    14                                                        22.5         3.95    25                                                        24.2         3.67    5                                                         24.8         3.59    4                                                         26.9         3.30    19                                                        28.7         3.11    7                                                         29.2         3.06    6                                                         30.0          2.976  5                                                         30.4          2.937  9                                                         31.7          2.823  7                                                         33.7          2.661  7                                                         34.4          2.605  10                                                        34.9          2.570  3                                                         36.7          2.448  5                                                         38.2          2.355  3                                                         45.4          2.000  3                                                         50.6          1.802  
 3.                                                       ______________________________________                                    

                  TABLE HB                                                         ______________________________________                                         (GaAPO-26)                                                                                          Relative Intensity                                        2Θ     d(Å)                                                                               100 × I/I.sub.o                                     ______________________________________                                          8.2         10.74   40                                                         9.8         9.06    7                                                         10.5         8.45    100                                                       14.3         6.20    3                                                         17.3         5.12    3                                                         17.8         4.99    4                                                         19.6         4.53    4                                                         21.9         4.06    6                                                         22.6         3.93    30                                                        26.9         3.32    6                                                         27.1         3.30    4                                                         27.7         3.22    3                                                         30.1          2.971  3                                                         30.5          2.927  4                                                         31.8          2.816  8                                                         33.8          2.652  3                                                         34.5          2.597  3                                                         35.0          2.564  
 3.                                                       ______________________________________                                    


21. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table I given in claim
 1. 22. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table J given in claim
 1. 23. The crystalline molecular sieves of claim 22 wherein the X-ray powder diffraction pattern set forth in Table J contains at least the d-spacings set forth in the following Table JA:

                  TABLE JA                                                         ______________________________________                                         (GaAPO-33)                                                                                          Relative Intensity                                        2Θ     d(Å)                                                                               100 × I/I.sub.o                                     ______________________________________                                          9.4         9.4     12                                                        12.7         6.96    64                                                        15.4         5.76    9                                                         17.1         5.20    16                                                        17.6         5.04    10                                                        18.1         4.90    3                                                         20.7         4.29    14                                                        21.0         4.23    3                                                         22.3         3.99    3                                                         23.0         3.87    5                                                         24.0         3.70    15                                                        26.2         3.40    17                                                        27.4         3.26    100                                                       29.7         3.01    7                                                         31.0          2.888  4                                                         32.1          2.785  5                                                         34.3          2.613  10                                                        38.2          2.359  3                                                         39.1          2.305  3                                                         46.9          1.938  4                                                         48.1          1.892  4                                                         51.9          1.762  3                                                         52.2          1.753  4                                                         52.6          1.740  6                                                         55.2          1.663  
 3.                                                       ______________________________________                                    


24. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table K given in claim
 1. 25. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table L given in claim
 1. 26. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table M given in claim
 1. 27. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table N given in claim
 1. 28. The crystalline molecular sieves of claim 27 wherein the X-ray powder diffraction pattern set forth in Table N contains at least the d-spacings set forth in the following Table NA:

                  TABLE NA                                                         ______________________________________                                         (GaAPO-36)                                                                                          Relative Intensity                                        2Θ     d(Å)                                                                               100 × I/I.sub.o                                     ______________________________________                                          7.8         11.3    100                                                        8.1         11.0    89                                                        16.4         5.40    40                                                        19.1         4.64    27                                                        27.6         3.24    13                                                        27.8         3.21    
 11.                                                      ______________________________________                                    


29. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table O given in claim
 1. 30. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table P given in claim
 1. 31. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table Q given in claim
 1. 32. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table R given in claim
 1. 33. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table S given in claim
 1. 34. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table T given in claim
 1. 35. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table U given in claim
 1. 36. The crystalline molecular sieves of claim 1, having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table V given in claim
 1. 37. Process for preparing crystalline molecular sieves having three-dimensional microporous framework structures of GaO₂, AlO₂ and PO₂ tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Ga.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Ga_(x) Al_(y) P_(z))O₂ and has a value of zero to about 0.3; and "x", "y" and "z" represent the mole fractions of gallium, aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the hexagonal compositional area defined by points A, B, C, D, E and F of FIG. 1, said crystalline molecular sieves having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of the following Tables A to V:

                  TABLE A                                                          ______________________________________                                         (GaAPO-5)                                                                      2Θ  d(Å)       Relative Intensity                                    ______________________________________                                          7.3-7.65  12.1-11.56    m-vs                                                  19.5-20.0 4.55-4.44      m-s                                                   20.9-21.3 4.25-4.17      m-vs                                                  22.2-22.7 4.00-3.92      w-vs                                                  25.7-26.2 3.47-3.40      w-m                                                   ______________________________________                                    

                  TABLE B                                                          ______________________________________                                         (GaAPO-11)                                                                     2Θ  d(Å)       Relative Intensity                                    ______________________________________                                          9.3-9.65 9.51-9.17      m-s                                                   20.2-20.6 4.40-4.31      m-s                                                   20.9-21.3 4.25-4.17      s-vs                                                  22.0-22.5 4.04-3.95      m-s                                                   22.5-22.9 3.95-3.92      m-s                                                   23.0-23.4 3.85-3.80      m-vs                                                  ______________________________________                                    

                  TABLE C                                                          ______________________________________                                         (GaAPO-14)                                                                     2Θ  d(Å)       Relative Intensity                                    ______________________________________                                         8.9-9.1   9.89-9.77      vs                                                    12.9-13.3 6.86-6.67      w-m                                                   15.7-15.8 5.66-5.61      w-m                                                   17.7-18.1 5.02-4.91      w-m                                                   22.2-22.8 4.00-3.89      w                                                     27.1-27.2 3.30-3.28      w                                                     ______________________________________                                    

                  TABLE D                                                          ______________________________________                                         (GaAPO-16)                                                                     2Θ   d(Å)      Relative Intensity                                    ______________________________________                                         11.3-11.6  7.83-7.63     m-vs                                                  18.7-18.9  4.75-4.70     w-s                                                   21.9-22.3  4.06-3.99     m-vs                                                  26.5-27.0  3.363-3.302   w-m                                                    29.7-30.05                                                                               3.008-2.974   w-m                                                   ______________________________________                                    

                  TABLE E                                                          ______________________________________                                         (GaAPO-17)                                                                     2Θ  d(Å)       Relative Intensity                                    ______________________________________                                         7.7-7.8   11.5-11.3      vs                                                    13.3-13.5 6.65-6.57      s-vs                                                  15.4-15.6 5.75-5.69      m-vs                                                  19.5-19.7 4.55-4.51      m-vs                                                  20.5-20.6 4.33-4.31      vs                                                    31.7-32.0 2.819-2.797    w-s                                                   ______________________________________                                    

                  TABLE F                                                          ______________________________________                                         (GaAPO-18)                                                                     2Θ   d(Å)      Relative Intensity                                    ______________________________________                                         9.5-9.7    9.27-9.14     vs                                                    15.5-15.7  5.73-5.64     w-m                                                   16.9-17.1  5.25-5.19     m                                                     20.15-20.25                                                                               4.41-4.39     m                                                     20.95-21.1 4.24-4.22     w-m                                                   31.8-32.5  2.814-2.755   m                                                     ______________________________________                                    

                  TABLE G                                                          ______________________________________                                         (GaAPO-20)                                                                     2Θ   d(Å)      Relative Intensity                                    ______________________________________                                          13.7-14.25                                                                               6.46-6.22     m-vs                                                  19.55-20.0 4.54-4.44     w-s                                                   24.05-24.6 3.70-3.63     m-vs                                                  28.3-28.5  3.16-3.13     w-m                                                   34.8-35.2  2.58-2.55     w                                                     ______________________________________                                    

                  TABLE H                                                          ______________________________________                                         (GaAPO-26)                                                                     2Θ  d(Å)       Relative Intensity                                    ______________________________________                                         8.2-8.3   10.8-10.7      w-vs                                                  9.6-9.9   9.2-9.0        vw-m                                                  10.5-10.6 8.45-8.35      w-vs                                                  21.8-22.1 4.07-4.01      w-vs                                                  22.5-22.7 3.95-3.92      w-s                                                   28.6-28.9 3.12-3.09      vw-m                                                  ______________________________________                                    

                  TABLE I                                                          ______________________________________                                         (GaAPO-31)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         8.5-8.6      10.40-10.28                                                                              m-s                                                     20.2-20.3    4.40-4.37 m                                                       21.9-22.1    4.06-4.02 w-m                                                     22.6-22.7    3.93-3.92 vs                                                      31.7-31.8    2.823-2.814                                                                              w-m                                                     ______________________________________                                    

                  TABLE J*                                                         ______________________________________                                         (GaAPO-33)                                                                     2Θ      d(Å) Relative Intensity                                      ______________________________________                                         9.25-9.55     9.56-9.26                                                                               w-m                                                     12.5-12.9     7.08-6.86                                                                               vs                                                      16.9-17.3     5.25-5.13                                                                               w-m                                                     20.45-20.9    4.34-4.25                                                                               w-m                                                     23.85-24.25   3.73-3.67                                                                               w-m                                                     26.05-26.35   3.42-3.38                                                                               w-m                                                     27.3-27.6     3.27-3.23                                                                               vs                                                      ______________________________________                                          *as-synthesized form                                                     

                  TABLE K*                                                         ______________________________________                                         (GaAPO-33)                                                                     2Θ      d(Å) Relative Intensity                                      ______________________________________                                         13.15-13.4    6.73-6.61                                                                               vs                                                      18.05-18.35   4.91-4.83                                                                               m                                                       18.4-18.6     4.82-4.77                                                                               m                                                       26.55-26.7    3.36-3.34                                                                               m                                                       32.0-32.1     2.80-2.79                                                                               m                                                       ______________________________________                                          *calcined form                                                           

                  TABLE L                                                          ______________________________________                                         (GaAPO-34)                                                                     2Θ      d(Å) Relative Intensity                                      ______________________________________                                          9.4-9.65     9.41-9.17                                                                               s-vs                                                    15.9-16.2     5.57-5.47                                                                               vw-m                                                    17.85-18.4    4.97-4.82                                                                               w-s                                                     20.3-20.9     4.37-4.25                                                                               m-vs                                                    24.95-25.4    3.57-3.51                                                                               vs-s                                                    30.3-30.8     2.95-2.90                                                                               w-s                                                     ______________________________________                                    

                  TABLE M                                                          ______________________________________                                         (GaAPO-35)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         10.8-11.1    8.19-7.97 m                                                       17.2-17.4    5.16-5.10 s-vs                                                     21.0-21.25  4.23-4.18 m-s                                                     21.8-22.0    4.08-4.04 vs                                                      31.8-32.2    2.814-2.788                                                                              m                                                       ______________________________________                                    

                  TABLE N                                                          ______________________________________                                         (GaAPO-36)                                                                     2Θ     d(Å) Relative Intensity                                       ______________________________________                                         7.7-7.9      11.5-11.2                                                                               vs                                                       16.2-16.6    5.47-5.34                                                                               w-m                                                      18.9-19.3    4.70-4.60                                                                               m-s                                                      27.4-27.7    3.26-3.22                                                                               w-m                                                      27.7-28.0    3.22-3.19                                                                               w-m                                                      ______________________________________                                    

                  TABLE O                                                          ______________________________________                                         (GaAPO-37)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         6.1-6.3      14.49-14.03                                                                              vs                                                      15.5-15.7    5.72-5.64 w-m                                                     18.5-18.8    4.80-4.72 w-m                                                     23.5-23.7    3.79-3.75 w-m                                                     26.9-27.1    3.31-3.29 w-m                                                     ______________________________________                                    

                  TABLE P                                                          ______________________________________                                         (GaAPO-39)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.4-9.6      9.4l-9.21                                                                               w-m                                                      13.3-13.6    6.66-6.51                                                                               m-vs                                                     18.0-18.4    4.93-4.82                                                                               m                                                        21.2-21.5    4.19-4.13                                                                               m-s                                                      22.5-23.0    3.95-3.87                                                                               s-vs                                                     30.2-30.5    2.96-2.93                                                                               w-m                                                      ______________________________________                                    

                  TABLE Q                                                          ______________________________________                                         (GaAPO-40)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.5-7.7      11.79-11.48                                                                              vw-m                                                    8.0-8.1      11.05-10.94                                                                              s-vs                                                    12.4-12.5    7.14-7.08 w-vs                                                    13.6-13.8    6.51-6.42 m-s                                                     14.0-14.1    6.33-6.28 w-m                                                     27.8-28.0    3.209-3.187                                                                              w-m                                                     ______________________________________                                    

                  TABLE R                                                          ______________________________________                                         (GaAPO-41)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         13.6-13.8    6.51-6.42 w-m                                                     20.5-20.6    4.33-4.31 w-m                                                     21.1-21.3    4.21-4.17 vs                                                      22.1-22.3    4.02-3.99 m-s                                                     22.8-23.0    3.90-3.86 m                                                       23.1-23.4    3.82-3.80 w-m                                                     25.5-25.9    3.493-3.440                                                                              w-m                                                     ______________________________________                                    

                  TABLE S                                                          ______________________________________                                         (GaAPO-42)                                                                     2Θ      d(Å)  Relative Intensity                                     ______________________________________                                         7.15-7.4      12.36-11.95                                                                              m-vs                                                    12.5-12.7    7.08-6.97 m-s                                                    21.75-21.9    4.09-4.06 m-s                                                     24.1-24.25   3.69-3.67 vs                                                     27.25-27.4    3.273-3.255                                                                              s                                                       30.05-30.25  2.974-2.955                                                                              m-s                                                    ______________________________________                                    

                  TABLE T                                                          ______________________________________                                         (GaAPO-44)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.4-9.55     9.41-9.26 vs                                                      13.0-13.1    6.81-6.76 w-m                                                     16.0-16.2    5.54-5.47 w-m                                                     20.6-20.85   4.31-4.26 s-vs                                                    24.3-24.4    3.66-3.65 w-vs                                                    30.7-30.95   2.912-2.889                                                                              w-s                                                     ______________________________________                                    

                  TABLE U                                                          ______________________________________                                         (GaAPO-46)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.2-8.1      12.3-10.9 vs                                                      21.2-21.8    4.19-4.08 w-m                                                     22.5-23.0    3.95-3.87 vw-m                                                    26.6-27.2    3.351-3.278                                                                              vw-w                                                    28.5-29.0    3.132-3.079                                                                              vw-w                                                    ______________________________________                                    

                  TABLE V                                                          ______________________________________                                         (GaAPO-47)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.4          9.41      vs                                                      15.9-16.0    5.57-5.54 w-m                                                     20.5-20.6    4.33-4.31 s                                                       24.5-24.7    3.63-3.60 w                                                       25.8-25.9    3.45-3.44 w                                                       30.4-30.5    2.940-2.931                                                                              w                                                       ______________________________________                                    

which process comprises providing a reaction mixture composition at an effective temperature and for an effective time sufficient to produce said molecular sieves, said reaction mixture composition being expressed in terms of molar oxide ratios as follows:

    aR:(Ga.sub.u Al.sub.v P.sub.w)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is an effective amount of "R" greater than zero; "b" has a value of from zero to about 500; and "u", "v" and "w" represent the mole fractions, respectively, of gallium, aluminum and phosphorus in the (Ga_(u) Al_(v) P_(w))O₂ constituent, and each has a value of at lest 0.01.
 38. Process according to claim 37 wherein "u", "v" and "w" are within the pentagonal compositional area defined by points K, G, H, I and J of FIG.
 3. 39. Process according to claim 37 wherein said reaction mixture composition comprises from about 0.2 to about 0.5 moles of Ga₂ O₃ per mole of P₂ O₅.
 40. Process according to claim 37 wherein said reaction mixture composition comprises from about 0.3 to about 1.0 mole of Al₂ O₃ per mole of P₂ O₅.
 41. Process according to claim 38 wherein "a" has a value greater than zero to about
 6. 42. Process according to claim 41 wherein "a" has a value not greater than about 1.0.
 43. Process according to claim 37 wherein "b" has a value of not greater than about
 20. 44. Process according to claim 37 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid.
 45. Process according to claim 37 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid and the source of aluminum is at least one compound selected from the group consisting of pseudo-boehmite and aluminum alkoxide.
 46. Process according to claim 45 wherein the aluminum alkoxide is aluminum isopropoxide.
 47. Process according to claim 37 wherein the source of gallium is selected from the group consisting of oxides, hydroxides, alkoxides, chlorides, bromides, iodides, sulfates, nitrates, carboxylates and mixtures thereof.
 48. Process according to claim 37 wherein the organic templating agent is a quaternary ammonium or quaternary phosphonium compound having the formula:

    R.sub.4 X.sup.+

wherein X is nitrogen or phosphorus and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms.
 49. Process according to claim 37 wherein the organic templating agent is an amine.
 50. Process according to claim 37 or claim 38 wherein the templating agent is selected from the group consisting of tetrapropylammonium ion; tetraethylammonium ion; tripropylamine; triethylamine; triethanolamine; piperidine; cyclohexylamine; 2-methyl pyridine; N,N-dimethylbenzylamine; N,N-dimethylethanolamine; choline; N,N-dimethylpiperazine; 1,4-diaziabicyclo-(2,2,2) octane; N-methyldiethanolamine; N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine; N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine; quinuclidine; N,N'-dimethyl-1,4 diazabicyclo (2,2,2) octane ion; tetramethylammonium ion; tetrabutylammonium ion; tetrapentylammonium ion; di-n-butylamine; neopentylamine; di-n-pentylamine; isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; 2-imidazolidone; di-n-propylamine; and a polymeric quaternary ammonium salt [(C₁₄ H₃₂ N₂)(OH)_(2]) _(x) wherein x is a value of a least
 2. 51. Molecular sieves prepared by calcining, at a temperature sufficiently high to remove at least some of the organic templating agent present in the intracrystalline pore system, the crystalline molecular sieves having three-dimensional microporous framework structures of GaO₂, AlO₂ and PO₂ tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Ga.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Ga_(x) Al_(y) P_(z))O₂ and has a value of zero to about 0.3; and "x", "y" and "z" represent the mole fractions of gallium, aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the hexagonal compositional area defined by points A, B, C, D, E and F of FIG. 1, said crystalline molecular sieves having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of the following Tables A to V:

                  TABLE A                                                          ______________________________________                                         (GaAPO-5)                                                                      2Θ     d(Å)  Relative Intensity                                      ______________________________________                                          7.3-7.65     12.1-11.56                                                                              m-vs                                                    19.5-20.0    4.55-4.44 m-s                                                     20.9-21.3    4.25-4.17 m-vs                                                    22.2-22.7    4.00-3.92 w-vs                                                    25.7-26.2    3.47-3.40 w-m                                                     ______________________________________                                    

                  TABLE B                                                          ______________________________________                                         GaAPO-11)                                                                      2Θ     d(Å) Relative Intensity                                       ______________________________________                                          9.3-9.65    9.51-9.17                                                                               m-s                                                      20.2-20.6    4.40-4.31                                                                               m-s                                                      20.9-21.3    4.25-4.17                                                                               s-vs                                                     22.0-22.5    4.04-3.95                                                                               m-s                                                      22.5-22.9    3.95-3.92                                                                               m-s                                                      23.0-23.4    3.85-3.80                                                                               m-vs                                                     ______________________________________                                    

                  TABLE C                                                          ______________________________________                                         (GaAPO-14)                                                                     2Θ     d(Å) Relative Intensity                                       ______________________________________                                         8.9-9.1      9.89-9.77                                                                               vs                                                       12.9-13.3    6.86-6.67                                                                               w-m                                                      15.7-15.8    5.66-5.61                                                                               w-m                                                      17.7-18.1    5.02-4.91                                                                               w-m                                                      22.2-22.8    4.00-3.89                                                                               w                                                        27.1-27.2    3.30-3.28                                                                               w                                                        ______________________________________                                    

                  TABLE D                                                          ______________________________________                                         (GaAPO-16)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         11.3-11.6    7.83-7.63 m-vs                                                    18.7-18.9    4.75-4.70 w-s                                                     21.9-22.3    4.06-3.99 m-vs                                                    26.5-27.0    3.363-3.302                                                                              w-m                                                      29.7-30.05  3.008-2.974                                                                              w-m                                                     ______________________________________                                    

                  TABLE E                                                          ______________________________________                                         (GaAPO-17)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.7-7.8      11.5-11.3 vs                                                      13.3-13.5    6.65-6.57 s-vs                                                    15.4-15.6    5.75-5.69 m-vs                                                    19.5-19.7    4.55-4.51 m-vs                                                    20.5-20.6    4.33-4.31 vs                                                      31.7-32.0    2.819-2.797                                                                              w-s                                                     ______________________________________                                    

                  TABLE F                                                          ______________________________________                                         (GaAPO-18)                                                                     2Θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.5-9.7      9.27-9.14 vs                                                      l5.5-15.7    5.73-5.64 w-m                                                     16.9-17.1    5.25-5.19 m                                                       20.15-20.25  4.41-4.39 m                                                       20.95-21.1   4.24-4.22 w-m                                                     31.8-32.5    2.814-2.755                                                                              m                                                       ______________________________________                                    

                  TABLE G                                                          ______________________________________                                         (GaAPO-20)                                                                     2θ   d(Å)       Relative Intensity                                   ______________________________________                                          13.7-14.25                                                                               6.46-6.22      m-vs                                                 19.55-20.0 4.54-4.44      w-s                                                  24.05-24.6 3.70-3.63      m-vs                                                 28.3-28.5  3.16-3.13      w-m                                                  34.8-35.2  2.58-2.55      w                                                    ______________________________________                                    

                  TABLE H                                                          ______________________________________                                         (GaAPO-26)                                                                     2θ   d(Å)       Relative Intensity                                   ______________________________________                                         8.2-8.3    10.8-10.7      w-vs                                                 9.6-9.9    9.2-9.0        vw-m                                                 10.5-10.6  8.45-8.35      w-vs                                                 21.8-22.1  4.07-4.01      w-vs                                                 22.5-22.7  3.95-3.92      w-s                                                  28.6-28.9  3.12-3.09      vw-m                                                 ______________________________________                                    

                  TABLE I                                                          ______________________________________                                         (GaAPO-31)                                                                     2θ   d(Å)       Relative Intensity                                   ______________________________________                                         8.5-8.6    10.40-10.28    m-s                                                  20.2-20.3  4.40-4.37      m                                                    21.9-22.1  4.06-4.02      w-m                                                  22.6-22.7  3.93-3.92      vs                                                   31.7-31.8  2.823-2.814    w-m                                                  ______________________________________                                    

                  TABLE J*                                                         ______________________________________                                         (GaAPO-33)                                                                     2θ   d(Å)       Relative Intensity                                   ______________________________________                                         9.25-9.55  9.56-9.26      w-m                                                  12.5-12.9  7.08-6.86      vs                                                   16.9-17.3  5.25-5.13      w-m                                                  20.45-20.9 4.34-4.25      w-m                                                  23.85-24.25                                                                               3.73-3.67      w-m                                                  26.05-26.35                                                                               3.42-3.38      w-m                                                  27.3-27.6  3.27-3.23      vs                                                   ______________________________________                                          *as-synthesized form                                                     

                  TABLE K*                                                         ______________________________________                                         (GaAPO-33)                                                                     2θ   d(Å)       Relative Intensity                                   ______________________________________                                         13.15-13.4 6.73-6.61      vs                                                   18.05-18.35                                                                               4.91-4.83      m                                                    18.4-18.6  4.82-4.77      m                                                    26.55-26.7 3.36-3.34      m                                                    32.0-32.1  2.80-2.79      m                                                    ______________________________________                                          *calcined form                                                           

                  TABLE L                                                          ______________________________________                                         (GaAPO-34)                                                                     2θ   d(Å)       Relative Intensity                                   ______________________________________                                          9.4-9.65  9.41-9.17      s-vs                                                 15.9-16.2  5.57-5.47      vw-m                                                 17.85-18.4 4.97-4.82      w-s                                                  20.3-20.9  4.37-4.25      m-vs                                                 24.95-25.4 3.57-3.51      vw-s                                                 30.3-30.8  2.95-2.90      w-s                                                  ______________________________________                                    

                  TABLE M                                                          ______________________________________                                         (GaAPO-35)                                                                     2θ   d(Å)       Relative Intensity                                   ______________________________________                                         10.8-11.1  8.19-7.97      m                                                    17.2-17.4  5.16-5.10      s-vs                                                  21.0-21.25                                                                               4.23-4.18      m-s                                                  21.8-22.0  4.08-4.04      vs                                                   31.8-32.2  2.814-2.788    m                                                    ______________________________________                                    

                  TABLE N                                                          ______________________________________                                         (GaAPO-36)                                                                     2θ   d(Å)       Relative Intensity                                   ______________________________________                                         7.7-7.9    11.5-11.2      vs                                                   16.2-16.6  5.47-5.34      w-m                                                  18.9-19.3  4.70-4.60      m-s                                                  27.4-27.7  3.26-3.22      w-m                                                  27.7-28.0  3.22-3.19      w-m                                                  ______________________________________                                    

                  TABLE O                                                          ______________________________________                                         (GaAPO-37)                                                                     2θ   d(Å)       Relative Intensity                                   ______________________________________                                         6.1-6.3    14.49-14.03    vs                                                   15.5-15.7  5.72-5.64      w-m                                                  18.5-18.8  4.80-4.72      w-m                                                  23.5-23.7  3.79-3.75      w-m                                                  26.9-27.1  3.31-3.29      w-m                                                  ______________________________________                                    

                  TABLE P                                                          ______________________________________                                         (GaAPO-39)                                                                     2θ   d(Å)       Relative Intensity                                   ______________________________________                                         9.4-9.6    9.41-9.21      w-m                                                  13.3-13.6  6.66-6.51      m-vs                                                 18.0-18.4  4.93-4.82      m                                                    21.2-21.5  4.19-4.13      m-s                                                  22.5-23.0  3.95-3.87      s-vs                                                 30.2-30.5  2.96-2.93      w-m                                                  ______________________________________                                    

                  TABLE Q                                                          ______________________________________                                         (GaAPO-40)                                                                     2θ   d(Å)       Relative Intensity                                   ______________________________________                                         7.5-7.7    11.79-11.48    vw-m                                                 8.0-8.1    11.05-10.94    s-vs                                                 12.4-12.5  7.14-7.08      w-vs                                                 13.6-13.8  6.51-6.42      m-s                                                  14.0-14.1  6.33-6.28      w-m                                                  27.8-28.0  3.209-3.187    w-m                                                  ______________________________________                                    

                  TABLE R                                                          ______________________________________                                         (GaAPO-41)                                                                     2θ   d(Å)       Relative Intensity                                   ______________________________________                                         13.6-13.8  6.51-6.42      w-m                                                  20.5-20.6  4.33-4.31      w-m                                                  21.1-21.3  4.21-4.17      vs                                                   22.1-22.3  4.02-3.99      m-s                                                  22.8-23.0  3.90-3.86      m                                                    23.1-23.4  3.82-3.80      w-m                                                  25.5-25.9  3.493-3.440    w-m                                                  ______________________________________                                    

                  TABLE S                                                          ______________________________________                                         (GaAPO-42)                                                                     2θ   d(Å)       Relative Intensity                                   ______________________________________                                         7.15-7.4   12.36-11.95    m-vs                                                 12.5-12.7  7.08-6.97      m-s                                                  21.75-21.9 4.09-4.06      m-s                                                   24.1-24.25                                                                               3.69-3.67      vs                                                   27.25-27.4 3.273-3.255    s                                                    30.05-30.25                                                                               2.974-2.955    m-s                                                  ______________________________________                                    

                  TABLE T                                                          ______________________________________                                         (GaAPO-44)                                                                     2θ   d(Å)       Relative Intensity                                   ______________________________________                                          9.4-9.55  9.41-9.26      vs                                                   13.0-13.1  6.81-6.76      w-m                                                  16.0-16.2  5.54-5.47      w-m                                                   20.6-20.85                                                                               4.31-4.26      s-vs                                                 24.3-24.4  3.66-3.65      w-vs                                                  30.7-30.95                                                                               2.912-2.889    w-s                                                  ______________________________________                                    

                  TABLE U                                                          ______________________________________                                         (GaAPO-46)                                                                     2θ   d(Å)       Relative Intensity                                   ______________________________________                                         7.2-8.1    12.3-10.9      vs                                                   21.2-21.8  4.19-4.08      w-m                                                  22.5-23.0  3.95-3.87      vw-m                                                 26.6-27.2  3.351-3.278    vw-w                                                 28.5-29.0  3.132-3.079    vw-w                                                 ______________________________________                                    

                  TABLE V                                                          ______________________________________                                         (GaAPO-47)                                                                     2θ   d(Å)       Relative Intensity                                   ______________________________________                                         9.4        9.41           vs                                                   15.9-16.0  5.57-5.54      w-m                                                  20.5-20.6  4.33-4.31      s                                                    24.5-24.7  3.63-3.60      w                                                    25.8-25.9  3.45-3.44      w                                                    30.4-30.5  2.940-2.931    w.                                                   ______________________________________                                     